REESE  LIBRARY 

OF  THK 

UNIVERSITY  OF  CALIFORNIA. 

.  .  &> 

/J.^  No. 


Accession  No 


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p 

U U L? 


ELECTROLYSIS 

AND 

ELECTROSYNTHESIS 


OF 


ORGANIC   COMPOUNDS. 


BY 


DR.  WALTHER    LOB, 

Privatdocent  in  the  University  of  Bonn. 


AUTHORIZED  TRANSLATION  FROM  THE  AUTHOR'S 
ENLARGED  AND  REVISED  EDITION 

BY 

H.    W.    F.    LORENZ,   A.M.,   Ph.D., 

Graduate  of  the  University  of  Berlin. 


FIRST  EDITION. 


NEW  YORK : 

JOHN    WILEY    &    SONS. 
LONDON  :   CHAPMAN  &  HALL,  LIMITED. 

1898. 


Copyright,   1898, 

BY 

H.   W.    F.   LORENZ. 


ROBERT   DRUMMOND,    rRINTER.    NEW  YORK. 


AUTHOR'S  PREFACE  TO  THE  AMERICAN 
EDITION. 


IN  the  two  and  a  half  years  that  have  passed  since 
the  appearance  of  the  first  edition  of  the  present 
work,  the  application  of  the  electric  current  in  organic 
chemistry  has  undergone  such  a  marked  development 
that  the  book  in  its  original  form  could  no  longer 
claim  to  give  an  adequate  idea  of  our  present  knowl- 
edge of  organic  electrolysis  and  electrosynthesis. 
During  these  last  two  years  in  particular  a  series  of 
important  researches  which  systematically  invade  this 
new  field  of  chemistry  have  been  brought  out  in  rapid 
succession. 

Since  I  am  now  engaged  in  the  preparation  of  a 
new  German  edition,  the  desire  of  Dr.  H.  W.  F. 
Lorenz  to  translate  the  book  affords  an  excellent 
opportunity  for  presenting  the  revised  and  completed 
edition  directly  to  his  fellow  countrymen.  I  hope 
that  his  excellent  translation  may  also  tend  to  draw 
the  attention  of  his  American  colleagues  to  this  broad 


IV  AUTHOR'S  PREFACE    TO   AMERICAN  EDITION. 

and  interesting  field,  and  that  electricity,  possessing 
such  a  diversity  of  applications,  may  soon  obtain  a 
recognized  position  in  organic  chemistry.  In  the 
realization  of  this  hope  the  author  and  translator  see 
a  rich  reward  for  their  efforts. 

Dr.  WALTHER  LOB. 

BONN,  June,  1898. 


TRANSLATOR'S  PREFACE. 


IN  presenting  this  excellent  little  work,  with  the 
permission  of  the  author,  to  the  English-reading 
public,  scarcely  anything  remains  to  be  added  to  what 
Dr.  Lob  has  already  said  in  his  prefaces  to  the  German 
and  American  editions.  He  has  read  the  manu- 
script and  made  the  necessary  changes  and  additions 
so  as  to  have  it  correspond  to  the  second  German 
edition  which  is  about  to  appear. 

The  translator  has  adhered  as  closely  as  possible  to 
the  original  text.  He  has  made  some  additions  and 
added  a  table  of  contents  and  a  complete  index,  which 
he  thinks  will  enhance  the  value  of  the  book. 

To  Dr.  B.  B.  Boltwood  of  the  Sheffield  Scientific 
School  of  Yale  University,  who  has  had  the  kind- 
ness to  revise  the  manuscript,  grateful  acknowledg- 
ments are  due  for  his  painstaking  and  valuable 
services. 

SPRINGFIELD,  OHIO, 
November,   1898. 


AUTHOR'S     PREFACE    TO    THE    FIRST 
GERMAN   EDITION. 


THE  object  of  electrochemistry  is,  among  others, 
that  of  performing,  with  the  aid  of  the  electric  current, 
reactions  which  have  up  to  the  present  been  carried 
out  by  the  employment  of  other  forms  of  energy. 
Its  very  nature  suggests  the  possibility  of  solving 
synthetical  and  analytical  problems  which  have  as  yet 
remained  unanswered.  In  this  respect  its  province  is 
both  that  of  inorganic  and  organic  chemistry.  Experi- 
ments have  recently  been  made  for  utilizing  electricity 
in  the  latter.  Few  only  of  the  many  tasks  presenting 
themselves  have  been  undertaken.  This  book  aims 
to  give,  as  briefly  as  possible,  a  review  of  what  has 
already  been  accomplished,  and  at  the  same  time  to 
create  an  interest  in  the  performance  of  experiments 
on  the  electrolysis  and  electrosynthesis  of  organic 
compounds. 

AACHEN, 

Electrotechnical  Laboratory 
of  the  Polytechnic  Institute. 
November.   1895. 

vi 


CONTENTS. 


INTRODUCTION xi 

I. 

ELECTROLYSIS    AND    ELECTROSYNTHESIS    OF 
ALIPHATIC    COMPOUNDS. 

i.  (a)  Hydroxyl  Compounds. 

Methyl  alcohol  —  Ethyl  alcohol  —  Propyl  alcohol  —  Butyl 
alcohol — (lodoform,  Chloroform,  Brornoform).  [Aristol, 
Nosophene.] 1-6 

Glycol — Glycerine — Glyceric  aldehyde — Chloral  hydrate — 
Hexatomic  alcohols  —  Mannite  —  Grape  sugar  —  Cane 
sugar — Dextrine — Gum  arable —  Collodion — Starch 6-10 

(b)  Ketones. 

Acetone  —  Chlor-acetones  —  Brom-acetones  —  Isonitroso-ace- 

tone — Acetyl-acetone 10-1 1 

(c}  Acids. 

Formic  acid — Formyl  chloride — Formamide — Acetic  acid — 
Kolbe's  experiments,  Kekule's  theory,  etc. — Rohland's 
experiments:  capronic,  caprylic  and  heptylk  acids,  unde- 
cylenic  and  oleic  acids — Acetic  acid,  continued — Chlor- 
acetic  acids — Cyan-acetic  acid — Thio-acetic  acid 1 1-20 

Propionic  acid — Butyric  acid;  isobutyric  acid,  Hamonet's 
conclusions — Valeric  acid — Capronic  acid — CEnanthylic 
acid 20-24 

Oxalic  acid — Malonic  acid — Succinic  acid — Glutaric  acid — 
Pyrotartaric  acid — Itaconic  acid — Citraconic  acid — Mesa- 
conic  acid — Malic  acid — Tartaric  acid — Bourgoin's  deduc- 
tions— KSkule;  maleic,  brom-malelc  and  fumaric  acids.. 25-31 


VUl  CONTENTS. 

EXPERIMENTS  OF  MILLER  AND  HOFER. 

(1)  Glycolic   acid— Ordinary   lactic   acid— Sarco-lactic   acid — 

a-Oxy-butyric  acid — a-Oxy-isobutyric  acid— Tartaric  acid 
— Hydracrylic  acid — /S-Oxy-butyric  acid— PhenyU/3-lactic 
acid — Methyl-glycolic  acid — Mandelic  acid— Glyceric  acid 
— Phenyl-glyceric  acid  —  Malic  acid  —  Racemic  acid — 
Ethyl-tartaric  acid 31-33 

(2)  Electrosy ntheses  :  Butyric  ethyl  ester — Succinic  ethyl  ester 

Capronic  and  isobutyl-acetic  ethyl  esters Ethyl  alco- 
hol— Ethyl  esters  of  propionic,  butyric,  and  valeric  acids 
— Ethyl-succinic  ester.  [<r-Methyl-hydrocinnamic  ester, 
Dibenzyl-succinic  ester.] 34~35 

Monobasic  oxy-acids.  [Mandelic  acid — Hydrobenzoin,  Iso- 

hydrobenzoin.]  Formation  of  aldehydes 35~36 

Oxy-acids — /7-Iodo-propionic  acid — Nitro-ethane 37 

ELECTROSYNTHESES  OF  BROWN  AND  WALKER. 

Formation  of  di-esters  of  dibasic  acids.  Succinic  acid  — 
Adipic  acid — Suberic  acid — Sebasic  acid — n-Dodecane- 
dicarboxylic  acid — n-Decahexane-dicarboxylic  acid 37-38 

Disubstituted  acids  :  Dimethyl-succinic  acids— Diethyl-suc- 
cinic  acids — Tetramethyl-succinic  acid — Methyl-acrylic 
acid — Ethyl-crotonic  acid.  [Campholytic  acid — Campho- 
thetic  acid — Allocampholytic  acid — Laurolene.] 38-42 

Electrolysis  of  ethyl-potassium  malonate  and  fumarate 42 

ELECTROSYNTHESES  OF  MULLIKEN  AND  WEEMS. 

Ethane-tetracarboxylic  ester — Ethane-hexacarboxylic  ester — 
Tetracetyl-ethane  —  Diacetyl-succinic  ester  —  Dimethyl- 
ethane-tetracarboxylic  ester  —  Diethyl-ethane-tetracar- 
boxylic  ester — Diacetyl-succinic  ester - 42-43 

Electrolysis  of  Acid  amides 43~44 

2.  Cyanogen  Compounds. 

Cyanogen — Hydrocyanic  acid,  electrolysis  and  electrosyn- 
thesis  of — Potassium  cyanide— Potassium  ferrocyanide— 
Potassium  ferricyanide-  Sodio-nitro-prusside— Prussian 
blue , , 44-46 

Reduction  of  nitriles — Aceto-nitrile — n-Propio-nitrile.  [Aro- 
matic nitriles — Benzo-nitrile  —  Benzyl-cyanide.] 46-47 


OF  THK 

UNIVERSITY 

x 


3.  Compounds  Containing  Sulphur. 

Mercaptans  —  Sulpho-compounds  —  Sodium  isethionate  - — 
Methyl-sulphuric  acid — Potassium-trichlorrmethyl  sul- 
phate —  Potassium-trichlor-methyl  sulphonate  —  Ethyl- 
sulphuric  acid — Potassium-isoamyl  sulphate — Potassium 
xanthate — Dimethyl-dithiocarbamic  acid 47~49 

Thiophene 49 

II. 

ELECTROLYSIS   AND    ELECTROSYNTHESIS    OF 
AROMATIC    COMPOUNDS. 

i.  Phenols. 
Phenol — Phenyl-mercaptan -51-53 

2.  Aldehydes  and  Ketones. 

Benzaldehyde — Michler's  ketone — Aceto-phenone — Benzile — 

Anthraquinone . 54~56 

(Nitro-aldehydes  and  ketones,  see  Nitro-Compounds.) 
3.  Acids. 

Benzoic  acid  —  Thio-benzoic  acid  —  Sulpho-benzoic  acid  — 
Phthalic  acid — Ethyl-potassium  phthalate — Phenyl-acetic 
acid — Cinnamic  acid — Benzyl-malonic  acid 56-58 

4.  Amido-Compounds. 
Aniline,  electrolytic  products  of 59-60 

INVESTIGATIONS  OF  GOPPELSROEDER. 

Preparation  of  aniline  black  from  aniline;  naphthylamine 
violet  from  naphthylamine  salts;  alizarine  from  anthra- 
quinone — Toluidene — Methyl-aniline  —  Diphenylamine — 
Methyl-diphenylamine — Naphthylamine 60-62 

Preparation  of  rosaniline,  crysaniline,  safranine,  and  p-lenk- 
aniline  —  Acetanilide  —  Amido-hydroquinone  —  Prepara- 
tion of  p-phenylene-diamine — Electrolysis  of  benzene — 
p-phenylene-diamine 62-63 

5.  Electrolytic  Reduction  of  Nitro-Compounds. 

Nitro-benzene — Nitro-phenol — N it ro-benzene-sul phonic  acid 
— o-Nitro-toluidene  —  Dinitro-benzene  —  o-p-Dinitro-tol- 
uene  —  p  -  Nitro-o- toluidene  —  m  -  Nitro-  ben  zoic  acid  — 


X  CONTENTS. 

. 

PAGE 

Nitro-toluic  acid  —  Nitro-terephthalic  acid  —  Nitro-iso- 
phthalic  acid — a,<23-Nitro-naphthalene-sulphonic  acid... 63-65 

Reaction  of  Gattermann  —  Nitro-toluenes — Nitro-r-xylene  — 
Lob's  experiments  —  Aromatic  nitramines  —  Nitro-car- 
boxylic  acids — Nitro-sulphonic  acids — Nitro-derivatives 
of  the  quinoline  series 66-70 

Nitro-aldehydes — Nitro-ketones — Nitro-acetophenone — Nitro- 

benzophenone — m-Nitro-phenyl-p-tolylketone 70-72 

p-Nitraniline — p-Nitro-phenol — Chlor-nitro-benzene  —  Nitro- 
toluene-sulphonic  acid — Dinitro-stilbene-disulphonic  acid 
— Dinitro-naphthalenes — Nitro-leuco-bodies 72-75 

Pyridine  —  Picoline — Nitro-piperidines — Nitroso-a-pipecoline 
—  Nitroso-aldehyde-capellidine  —  Quinoline  —  Quinal- 
dine 75~76 

6.  Electrolytic  Oxidation  of  Nitro-Compounds. 

Nitroso-piperidine  —  Nitro-toluene  —  Azo-benzene,  introduc- 
tion of  hydroxyl  groups  —  Toluene-sulphone-amides — 
Saccharine — p-Nitro-o-toluene-sulphone  -  amide — Oxida  - 
tion  of  aromatic  oxy-carboxylic  acids 76-78 

7.  Electrolysis  of  Alkaloids. 

(Caffeine,  Theme) — Atropine — Opium — Morphine— Codeine— 
Cotarnine  —  Quinine  —  Cinchonine  —  Strychnine  —  Bru- 
cine 78-80 

8.  Camphor  and  Glucosides. 

Terpentine  hydrochloride 80 

Salicine 81 

9.  Electrolysis  of  Blood 81 

10.  Electrolysis  of  Albumen 81-82 

II.  Electrolysis  and  Electrosynthesis  with  Alternating 
Currents. 

Dehydration.       Ammonium     carbamate  —  Phenol-sulphuric 

acid — Phenol — Capronic  acid 82-86 

LIST  OF  AUTHORS 87 

INDEX 91 


INTRODUCTION. 


WHILE  the  electrolysis  of  inorganic  compounds  has 
already  obtained  a  recognized  position  in  pure  and 
applied  science,  the  action  of  the  electric  current,  as 
a  productive  means  for  carrying  out  the  synthesis  or 
decomposition  of  organic  substances,  has  not  given 
results  which  are  entirely  satisfactory.  The  reason 
for  this  lies  in  the  great  difficulty  that  is  encountered 
in  investigations  aimed  in  this  direction  by  the  ap- 
pearance of  secondary,  complicated  processes  in  the 
cell,  in  contrast  to  the  gen-  rally  simple  decomposi- 
tions of  inorganic  compounds  by  the  electric  current. 
The  very  different  conditions  required  for  inorganic 
and  organic  electrolysis  give  a  distinctive  character  to 
the  history  of  these  two  branches.  In  inorganic 
electrolysis  one  investigation  follows  as  a  continuation 
of  those  preceding  it.  The  later  investigators  stand 
upon  the  shoulders  of  their  predecessors.  A  sys- 
tematic and  regular  development  is  the  result.  The 
case  is  different  in  organic  electrolysis,  Difficulties 

which  were  seldom  surmounted  have  caused  each  in- 

xi 


Xll  1NTROD  UCTION. 

vestigator  wishing  to  arrive  at  profitable  results  to 
attack  the  problem  from  a  new  standpoint.  Its  his- 
tory, therefore,  is  not  that  of  a  gradual  development, 
but  consists  of  many,  in  great  part  incoherent,  facts. 
This  characteristic  is  plainly  reflected  in  the  litera- 
ture. Scattered  in  all  possible  periodicals  are  found 
researches  which,  although  having  the  same  end  in 
view,  frequently  diverge  considerably  in  their  results. 
While  engaged  in  investigations  on  organic  electroly- 
sis and  electrosynthesis,  I  undertook  to  compile  the 
literature  on  the  subject  as  completely  as  possible,  at 
first  only  for  my  own  guidance.  On  the  supposition 
that  it  may  be  of  service  to  some  fellow  investigator 
I  publish  this  resumed  Considering  the  difficulty  of 
becoming  acquainted  with  the  entire  literature  of  this 
field,  this  publication  does  not  claim  to  possess  an 
exhaustive  completeness.  I  hope,  however,  that 
nothing  of  importance  has  been  overlooked.  While 
in  inorganic  electrolysis  chief  attention  is  given  to  the 
primary  processes  in  the  cell,  in  organic  electrolysis 
the  secondary  actions  claim  our  special  interest,  since 
the  factors  which  are  chiefly  active  in  effecting  the 
synthesis  or  decomposition  of  organic  compounds, 
i.e.,  hydrogen,  oxygen,  etc.,  are  the  result  of  a 
primary  decomposition  of  the  organic  electrolyte.  In 
a  systematic  description  of  the  results  obtained  it 
would  therefore  be  better  for  the  sake  of  clearness 
not  to  consider  the  actual  electrolytic  processes,  but 


INTRODUCTION.  Xill 

to  make  a  division,  according  to  the  final  chemical 
products,  into  oxidation,  reduction,  substitution  or 
addition,  and  condensation  reactions.  But  here  we 
are  confronted  by  the  difficulty  that  frequently  sev- 
eral different  processes  occur  at  the  same  time, 
making  the  indicated  classification  difficult  to  accom- 
plish. I  regard  it  as  the  simplest  method  to  treat 
the  subject  in  accordance  with  the  chemical  character 
of  the  electrolytes. 


ELECTROLYSIS  AND  ELECTROSYNTHESIS 
OF  ALIPHATIC  COMPOUNDS. 


I.  (a)  Hydroxyl  Compounds. 

The  investigations  on  the  behavior  of  the  mon- 
atomic  alcohols  have  been  confined  almost  entirely  to 
methyl  and  ethyl  alcohol,  both  of  which  show  com- 
plete analogy  in  their  reactions.  In  those  cases  where 
platinum  electrodes  were  used  and  similar  results  were 
obtained  both  with  and  without  porous  separating 
cells,  the  decompositions  are  almost  without  excep- 
tion oxidation  processes.  Being  in  the  pure  state 
poor  conductors,  the  alcohols  require  strong  currents 
for  their  electrolysis.  The  addition  of  potassium  car- 
bonate or  dilute  acid  increases  the  conductivity  of  the 
solution,  but  of  course  influences  the  results. 

The  manner  in  which  the  primarily  formed  decom- 
position products,  oxygen  and  hydrogen,  act  in  the 
simplest  case,  i.e.,  in  aqueous  solution,  depends  solely 
upon  the  chemical  constitution  of  the  electrolytes. 
It  is  evident,  therefore,  that  in  the  electrolysis  of  ali- 


2          ELECTROLYSIS  AND   ELECTROS YNTffESIS 

phatic  hydroxyl  compounds,  only  oxidation  products 
will  appear.  In  fact  hydrogen  is  evolved  at  the 
negative  pole,  while  the  greater  part  of  the  oxygen  is 
absorbed. 

The  first  attempts  to  electrolyze  alcohols  were  con- 
fined to  the  action  of  the  electric  spark  from  an  in- 
duction apparatus  on  the  vapor  of  an  alcohol.  By 
thus  treating  ethyl  alcohol  M.  Quet  *  and  Perrot2 
obtained,  besides  some  carbon,  a  substance  which  ex- 
ploded on  being  heated,  the  chemical  nature  of  which 
they  were  unable  to  determine.  Perrot  found  that 
no  water  was  formed  in  the  decomposition  of  the 
alcohol;  he  was  also  unable  to  prove  the  presence  of 
carbonic  acid  gas.  Maquenne3  obtained  a  gas  which 
possessed  a  strong  aldehydic  odor,  and  contained 
hydrogen,  ethane,  ethylene,  acetylene,  carbon  mon- 
oxide, and  carbon  dioxide. 

The  results  obtained  by  the  use  of  direct  currents 
were  much  more  satisfactory  than  the  above.  We 
are  indebted  to  Renard,4  Almeida  and  Deh£rain, 
Jaillard,'  and  Habermann7  for  the  most  thorough  ex- 
periments on  this  subject. 

Methyl  Alcohol. — The  results  obtained  with  methyl 
alcohol  can  be  summed  up  as  follows:  Hydrogen 
being  evolved,  the  oxidation  products  formed  are: 

1  Comp.  rend.,  46,  903.  s  Comp.  rend.,  46,  180. 

8  Bull.  soc.  chim.,  37,  298.  4  Comp.  rend.,  80,  105,  236. 

5  Comp.  rend.,  51,  214.  '  Comp.  rend.,  58,  203. 
*  Monatsch.  Wien,  7,  259. 


OF  A  LIP  HA  7^  1C  COMPOUNDS.  3 

1.  In    aqueous    sulphuric    acid    solution:     methyl 
formate,   methylal,   methyl  acetate,  acetic  acid,   and 
methyl-sulphuric   acid,   a  little   carbon    dioxide   and 
monoxide,  but  no  formic  aldehyde. 

Renard  considers   the   formation  of  acetic  acid  as 
due  to  reciprocal  action  between  the  alcohol 
bon  monoxide, 

CH3OH  +  CO  =  CH3.COOH. 

Jahn '  thinks  the  formation  must  be  traceable  to  the 
presence  of  ethyl  alcohol. 

2.  In  aqueous  solution,  on  the  addition  of  potas- 
sium  acetate   (Habermann):    besides  carbon   dioxide 
and  carbon  monoxide,  methane  and  potassium  methyl- 
carbonate. 

3.  Without  a  solvent,  by  itself  or  with  the  addition 
of  a  little  alkali:    chiefly  potassium  carbonate;    also 
hydrogen,    oxygen,    carbon    monoxide,    and    carbon 
dioxide. 

Ethyl  Alcohol. — In  the  case  of  this  alcohol  the  more 
important  results  have  been  obtained  by  the  investi- 
gators above  mentioned.  Schonbein  a  and  Becquerel s 
later  also  carried  out  some  investigations  on  the  same 
subject.  The  results  of  the  researches  are,  in  general, 
that  the  final  products  formed  are  the  following: 

1  Jahn,  Grundriss  d.  Elektrochemie,  1894,  p.  291. 
9  Tommasi,  Traite  d'Electrochimie,  1889,  p.  726. 
8  Comp.  rend.,  81,  1002,  and  various  other  places  in  the  same 
journal  ;  Tommasi,  Traite  d'Electroch.,  1889,  p.  726. 


4         ELECTROLYSIS  AND    EL  EC  TROS  YN  THESIS 

1.  In    sulphuric    acid    solution:    aldehyde,    acetic 
ester,     formic     ester,     ethylidene     oxy-ethyl     ether 

— CH^°£H)     (Renard)    and     ethyl-sulphuric 

acid. 

2.  Almeida  and  Deherain  state  that    in   the   elec- 
trolysis  of  a  nitric  acid  solution  they  observed,   in 
addition   to   these  oxidation   products,   carbonaceous 
derivatives  of  ammonia  at  the  negative  pole. 

3.  In  hydrochloric  acid  solution,1  chlor-acetic  acids 
occur  in  addition  to  the  corresponding  oxidation  pro- 
ducts  (Riche8).       Habermann,    on   electrolyzing    the 
alcohol  in  alkaline  solution,  obtained,  besides  carbon 
dioxide,    an  aldehyde    resin    (Ludersdorf3   and    Con- 
nel 4)  from  which  he  isolated  a  body  closely  related 
to  cinnamic  aldehyde.     In  aqueous  solution,  on  the 
addition  of  potassium  acetate,  the  alcohol  was  split 
up   into    ethane,    potassium   ethyl-carbonate,    carbon 
dioxide,    and   acetic    ester.      Also    with  propyl   and 
butyl  alcohols,  to  which  potassium  acetate  had  been 
added,    analogous    results  were  obtained   by  Haber- 
mann. 

Exact  statements    regarding  the   strength    of   the 
current  are  in  no  case  given.      In  consideration  of  the 


1  Pogg.  Ann.,  19,  77. 

8  Tommasi,  Trait6  d'Electrochimie,  1889,  728. 

3  Pogg.  Ann.,  19,  77. 

4  Pogg.  Ann.,  36,  487;  Phil.  Mag.,  18,  47. 


OF  ALIPHATIC  COMPOUNDS.  5 

importance  of  these  data  and  the  fact  that  the  result 
of  the  electrolysis  is  dependent  upon  the  density  and 
potential  of  the  electric  current  and  the  influence  of 
the  dissociative  power  of  solutions,  a  strong  incentive 
for  repeating  the  experiments,  with  the  help  of 
modern  scientific  and  technical  advancement,  is 
offered  to  the  investigator. 

lodoform*  —  The  complete  conversion  of  ethyl  alco- 
hol into  iodoform  by  electrolysis  in  alkaline  iodide 
solution  is  a  process  now  made  use  of  in  industrial 
chemistry.  The  course  of  the  reaction  is  illustrated 
by  the  equation  (K.  Elbs2  and  Herz8) 

CHSCH2OH  +  10!  +  H20  =  Ci}-  CO,  +  ;HI. 


The  electrolysis  is  best  performed  as  follows:  A 
solution  of  10-15  g-  calcined  soda  and  10  g.  potas- 
sium iodide  in  100  cc.  water  and  20  cc.  alcohol  is 
placed  in  a  porous  earthenware  cylinder  with  platinum 
anode.  The  cathode,  of  nickel,  is  surrounded  by  a 
strong  solution  of  sodium  hydroxide.  The  electroly- 
sis is  carried  out  at  a  temperature  of  70°  C.,  with  a 
current  density  at  the  anode  of  I  amp.  per  100  sq. 
cm.,  and  is  continued  for  2-4  hours. 

After  standing  for  several  hours  iodoform  crystal- 
lizes from  the  solution,  the  current  yield  being  60- 

1  German  Patent,  29,771. 

2  Ztschr.  f.  Elektroch.,  4,  113. 

8  Oettel,  Elektroch.  Uebungsaufg.,  1897,  p.  53. 


O         ELECTROLYSIS  AND   ELECTROS YNTHESIS 

70$.     Sodium  iodide  remains  in  the  mother-liquor  as 
the  principal  secondary  product. 

Chloroform  and  Bromoform  are  formed  if  the  chlo- 
ride or  bromide  of  the  alkalies  is  used  (comp.  Elbs 
and  Herz,1  who  deny  this*).  Analogous  to  these  sub- 
stitution reactions  is  the  formation  of  aristol?  a  di-thy- 
mol-di-iodide,  as  made  by  Messinger  and  Vortmann,9 
by  the  electrolysis  of  thymol  with  the  addition  of 
potassium  iodide.  Similar  to  this  also  is  the  pre- 
paration of  nosophene,  a  tetra-iodo-phenol-phthalein 
(Classen  and  Lob4). 

Glycol. — Of  diatomic  alcohols  only  glycol  seems  to 
have  been  the  subject  of  investigation.  Renard 6 
observed  in  the  electrolysis  of  a  sulphuric  acid  solu- 
tion of  glycol,  besides  the  formation  of  hydrogen, 
carbon  monoxide,  carbon  dioxide,  and  oxygen,  that 
trioxy-methylene,  glycolic  acid,  formic  acid,  and  a 
substance  isomeric  with  glucose  were  present  in  the 
solution. 

Ethylene  Glycol  under  similar  conditions  gives  the 
same  products  (Renard  6). 

Glycerine. — Renard  "also  investigated  the  behavior 

Zeitschr.  Elektroch.,  4,  118. 
German  patent,  64405. 
German  patent,  64405;  Lum.  61.,  52,  226. 
Chem.  Ber.,  28,  1603. 

Traite  d'Electrochimie  p.  Tommasi,  1889,  p.  730. 
Ann.  chim.  phys.,  [5]  17,  303,  313;  Comp.  rend.,  8l,  188;  ibid., 
82,  562. 

*  Translator. 


OF  ALIPHATIC  COMPOUNDS.  7 

of  glycerine.  In  the  electrolysis  of  a  dilute  sulphuric 
acid  solution  he  obtained  besides  the  gases,  hydrogen, 
oxygen,  carbon  monoxide  and  dioxide, — trioxy- 
methylene,  formic  acid,  acetic  acid,  glyceric  aldehyde, 
and  a  body  to  whose  barium  compound  he  gave  the 
formula  (C3H3O4)2Ba  (glyceric  acid?). 

Further  electrolysis  of  glyceric  aldehyde  gave  the 
ordinary  oxidation  products,  and,  as  in  the  case  of 
glycol,  a  substance  closely  related  to  ordinary  glucose. 
Bartoli  and  Papasogli  1  repeated  these  experiments, 
varying  the  material  of  the  electrodes,  and  obtained 
the  following  results: 

Carbon  anode  and  platinum  cathode  gave  trioxy- 
methylene,  formic  acid,  glyceric  acid,  a  substance 
similar  to  glucose,  and  a  resin. 

Graphite  and  platinum  electrodes  yielded  the  same 
products,  but  a  larger  per  cent  of  formic  acid  was 
formed  on  using  the  latter.  The  alkaline  solution 
of  glycerine,  electrolyzed  by  Stone  and  McCoy,3 
gave  condensation  products  of  glyceric  aldehyde 
similar  to  those  which  have  been  obtained  in  the 
synthesis  of  glucose.  Glyceric  acid  also  was  found 
present. 

Tommasi 8  electrolyzed  a  sulphuric  acid  solution  of 
chloral  hydrate  and  was  able  to  prove  the  presence  of 
hydrochloric  acid.  On  working  with  isolated  elec- 

1  Gazz.  chim.,  13,  287.  a  Amer.  Chem.  Journ.,  15,  656. 

8  Tommasi,  TraitS  d'Electrochimie,  1889,  p.  741. 


5         ELECTROLYSIS  AND   ELECTROS 'YN THESIS 

trodes,  an  abundance  of  chlorine  was  given  off  at  the 
cathode  and  acetic  aldehyde  collected  at  the  anode. 

Hexatomic  Alcohols. — The  decomposition  phenom- 
ena of  hexatomic  alcohols  and  sugars  are  similar  to 
those  of  glycerine.  A  part  is  completely  oxidized 
either  to  carbon  monoxide  and  carbon  dioxide  or  to 
formic  acid,  while  the  remainder,  on  timely  interrup- 
tion of  the  experiment,  gives  lower  oxidation  products 
which  vary  with  the  configuration  of  the  alcohols  and 
sugars. 

Mannite.1 — In  the  electrolyzed  fluid  from  mannite 
Renard  obtained  formic  acid,  trioxy-methylene,  ox- 
alic acid,  a  sugar  isomeric  with  glucose,  and  an  acid, 
C,H8O8,  which  he  regarded  as  the  aldehyde  of  sac- 
charic acid.  He  could  detect  no  mannonic  acid. 

Grape  Sugar. — This  sugar,  investigated  by  Renard, 
on  being  subjected  to  the  action  of  the  current  broke 
up  into  carbon  monoxide,  carbon  dioxide,  formic 
acid,  trioxymethylene,  and  saccharic  acid. 

Cane  Sugar. — Brester a  found  on  electrolyzing  cane 
sugar  that  the  solution  turns  strongly  acid  and  pos- 
sesses reducing  properties,  very  little  carbon  dioxide 
being  given  off.  He  was  not  able  to  determine  the 
nature  of  the  substance  which  he  isolated  by  distilla- 
tion and  which  was  free  from  formic  and  acetic  acid. 
On  further  electrolysis  it  gave  the  usual  final  oxida- 

1  Ann.  chim.  phys.,  [5]  17,  289. 
*  Bull.  soc.  chim.,  8,  23. 


OF  ALIPHATIC  COMPOUNDS.  9 

tion  products.  The  experiments  made  by  the  same 
author  on  the  electrolysis  of  dextrine,  gum  arable, 
collodion,  and  starch  gave  no  noteworthy  results. 

The  general  impression  gained  from  the  investiga- 
tions of  the  alcohols,  aldehydes,  and  alcohol-aldehydes 
mentioned,  is  that  the  general  reaction  is  one  of  suc- 
cessive oxidation.  The  electrolytic  oxygen  gradually 
oxidizes  the  substances,  the  final  product  being  car- 
bon dioxide.  Intermediate  products  are  formed, 
their  quantity  depending  upon  the  duration  of  the 
electrolysis.  In  following  these  processes  it  is  of 
especial  importance  whether  the  oxidation  products 
are  soluble  or  insoluble  and  whether  they  are  electro- 
lytes or  not.  The  possibility  of  isolating  the  products 
which  are  formed  depends  on  these  properties.  If 
the  product  of  oxidation  first  formed  is  a  good  con- 
ductor of  the  electric  current  it  will,  of  course,  undergo 
further  oxidation;  if  it  is  insoluble  it  escapes  the 
further  action  of  the  current.  In  order,  therefore,  to 
obtain  a  comprehensive  idea  of  the  decomposition  of 
organic  substances  it  is  necessary  immediately  to 
withdraw  the  electrolyzed  fluid  from  the  action  of  the 
current.  Miller  and  Hofer1  accomplished  this  by 
allowing  the  solution  to  flow  slowly  over  the  elec- 
trodes. But  very  few  experiments  of  this  nature  have 
been  made.  Mannite  serves  as  an  illustration  of  such 
an  oxidation  process.  As  already  mentioned,  it 
1  Chem.  Ber.,  27,  461. 


10       ELECTROLYSIS  AND   ELECTROS YN THESIS 

breaks  up  into  formic  acid,  oxalic  acid,  a  sugar,  and 
an  acid,  C6H8O8.  The  reactions  are  probably  the  fol- 
lowing: 

C6HM06  -4  C.H.A  -»  C3H609-»  C8H808 
->  CHaO3  -»  CaHaO4  ->  CO  -»  CO2. 

Whether  any  intermediate  products  have  escaped 
observation,  and  the  nature  of  these,  can  naturally  be 
determined  only  by  new  and  careful  experiments. 

Since  organic  substances,  apart  from  acids,  bases, 
and  salts,  are  poor  conductors  of  electricity,  the  addi- 
tion of  a  mineral  acid  to  an  organic  electrolyte  pro- 
duces a  complication  of  conditions,  since  oxidation 
reactions  occur  in  combination  with  substitutions. 
After  it  is  once  made  possible  to  establish  and  regu- 
late the  oxidizing  and  reducing  effects  of  the  current, 
the  field  of  substitution  reactions  is  the  one  which 
offers  the  most  promising  results. 

(b)  Ketones. 

Acetone. — Acetone  has  been  electro lyzed  by  Mul- 
der,1 Riche,*  and  Friedel.1  The  electrolysis  of  an 
acetone  solution  acidified  with  sulphuric  acid  gave 
carbon  dioxide,  acetic  acid,  and  formic  acid.  In 
hydrocloric  acid  solution  mono-chlor-acetone  and  di- 
chlor-acetone  could  be  isolated;  in  hydrobromic  acid 

1  Jahresber.  f.  Chemie,  1859,  p.  339. 

1  Comp.  rend.,  49,  176. 

*  Ann.  Chem.  Phar.,  112,  376. 


OF  ALIPHATIC  COMPOUNDS.  II 

solution  mono-brom-acetone.  Wilde  '  investigated  the 
action  of  the  electric  spark  on  acetone  vapor  in 
Torricelli's  vacuum.  Acetylene  was  formed  in  the 
gas  mixture  and  carbon  was  deposited  on  the  sides  of 
the  vessel.  According  to  Maquenne  *  acetone  vapor 
is  decomposed  by  the  electric  discharge  into  hy- 
drogen, ethane,  and  carbon  monoxide,  a  small  quantity 
of  acetylene  and  carbon  dioxide  being  formed.  On 
the  other  hand,  Hemptinne*  syntheticized  both  ace- 
tone and  aldehyde  by  passing  a  silent  electric  dis- 
charge through  a  mixture  of  carbon  monoxide  and 
ethane,  the  gases  being  kept  cool  by  the  use  of  a 
freezing  mixture. 

Isonitroso-acetone. — Ahrens  and  Meissner4  tried  to 
reduce  this  compound  electrolytically  to  amido- 
acetone.  They,  however,  obtained  dimethyl-pyra- 
zine,  ketine,  C,H8N,,  in  small  quantity. 

Acetyl-acetone.6  —  Acetyl-acetone  in  an  alcoholic 
solution  on  electrolysis  gave  tetracetyl-^. 

THH        ^ 

Acids.         I  UNIVERSITY 

The  investigation  of  acids  has  beefr^much-^nlore 
extensive  than  that  of  those  classes  of  bodies  which 
have  been  thus  far  discussed.  The  conditions  here 

1  Bull.  soc.  chim.,  [2]  5,  267. 

*  Bull.  soc.  chim.,  39,  306;  ibid.t  40,  60. 

1  Bull.  Acad.  roy.  Beige,  [3]  34,  269. 

4  Chem.  Ber.,  30,  532. 

6  Ahrens,  Handb.  d.  Cheoiie,  p.  482  (1896). 


12       ELECTROLYSIS  AND   ELE CTROS YN THESIS 

are  much  simpler,  since  the  acids  are  mostly  good 
conductors  of  electricity,  both  in  solution  and  in 
the  free  condition,  as  well  as  in  the  form  of  salts. 
Kolbe's '  classical  investigations  on  the  electrolysis  of 
organic  compounds,  in  which  he  demonstrated  the 
formation  of  the  hydrocarbons  from  the  acids,  are  the 
foundation  of  later  investigations.  A  continuation 
along  the  same  line  are  the  researches  of  Kekule,a 
Brown  and  Walker,3  Mulliken,4  and  Weems.5  They 
employed  the  electric  current  as  a  valuable  means  for 
effecting  the  synthesis  of  a  complete  series  of  com- 
pounds. 

For  the  sake  of  clearness  the  researches  here  given 
will  be  arranged  chiefly  in  accordance  with  their 
chemical  characteristics. 

Formic  Acid. — Although  up  to  this  point,  in  the  in- 
vestigations mentioned,  it  has  been  necessary  to  con- 
sider chiefly  oxidizing  reactions,  we  now  enter  upon  a 
field  comprising  those  reactions  which  involve  the 
process  of  reduction,  and  in  which  compounds  of  a 
relatively  high  stage  of  oxidation  are  the  starting- 
points.  The  electrolytic  formation  of  formic  acid 
from  oxalic  acid,  as  observed  by  Royer,6  is  a  reduc- 
tion reaction  of  this  nature. 

1  Lieb.  Ann.,  69,  257. 

8  Lieb.  Ann.,  131,  79. 

8  Lieb.  Ann.,  261,  107. 

4  Amer.  Chem.  Journ.,  15,  523. 

6  Amer.  Chem.  Journ.,  16,  569. 

6  Comp.  rend.,  70,  731;  Bull.  soc.  chim.,  [2]  14,  226. 


OF  A  L  IP  HA  TIC  COMPO  UND  S.  1 3 

Wilde1  found  that  the  action  of  the  electric  spark 
on  gaseous  mixtures  of  oxygen  and  alcohol,  hydrogen 
and  carbon  dioxide,  methane  and  carbon  dioxide  pro- 
duced formic  acid.  Losanitsch  and  Jovitschitsch8 
obtained  formic  acid  by  treating  carbon  monoxide  or 
dioxide  and  water  in  Berthelot's  ozone  apparatus. 
The  behavior  of  the  acid  itself  as  well  as  its  salts  has 
been  made  the  subject  of  thorough  investigation  car- 
ried out  chiefly  by  Brester,3  Renard*  and  Bourgoin,6 
Bartoli  and  Papasogli.8 

The  progress  of  the  decomposition  is  accompanied 
by  the  evolution  of  carbon  dioxide  and  oxygen  at  the 
positive  pole  and  hydrogen  at  the  negative  pole.  The 
quantitative  relations  of  the  decomposition  products 
vary  with  the  concentration  of  the  solution  and  the 
density  of  the  current.  The  reactions  occur  accord- 
ing to  the  following  equations: 

HCOOH  =  HCOO  +  H, 
HCOO  +  HCOO  =  Ha  +  2COa, 
2HCOO  +  H3O  =  2HCOOH  +  O. 

It  is  therefore  theoretically  impossible  to  effect  the 
complete  decomposition  of  the  formic  acid  present. 
In  the  electrolysis  of  sodium  formate,  carbon  dioxide 

Bull.  soc.  chim.,  [2]  5,  267. 
Chem.  Ber.,  30,  135. 
Zeitsohr.  f.  Chemie,  1866,  p.  60. 
Ann.  chim.  phys.,  [5]  17,  289. 
Ann.  chim.  phys.,  [4]  14,  157. 
Gazz.  chim.,  13,  22  and  88. 


14       ELECTROLYSIS  AND   ELECTROS YN THESIS 

and  formic  acid  are  in  fact  always  formed  at  the  posi- 
tive pole  and  hydrogen  and  sodium  hydroxide  at  the 
negative  pole.  The  discussion  of  the  other  salts  is 
unnecessary  since  their  behavior  is  quite  analogous. 

For  my  I  Chloride  (?)  has  been  obtained  by  Losanitsch 
and  Jovitschitsch  from  a  mixture  of  carbon  monoxide 
and  hydrochloric  acid  by  the  action  of  the  electric 
discharge,  and  by  a  like  method  formamide  has  been 
prepared  from  carbon  monoxide  and  ammonia. 

Acetic  Acid. — Acetic  acid  is  formed  in  the  electroly- 
sis of  methyl  and  ethyl  alcohol  when  the  electric 
spark  is  passed  through  a  mixture  of  alcohol  vapor 
and  oxygen,  or  methane  and  carbon  dioxide.  On  the 
other  hand  acetic  acid  can  be  converted  into  alcohol 
by  electrolytic  reduction,  if  the  acid  is  substituted  in 
place  of  nitric  acid  in  the  porous  cup  of  a  Bunsen 
element.1 

Glacial  acetic  acid  is  a  poor  conductor  of  electricity. 
According  to  Lapschin  and  Tichanowitsch a  its  decom- 
position when  effected  with  the  use  of  900  Bunsen 
elements  yields  at  the  anode,  carbon  monoxide  and 
carbon  dioxide;  at  the  cathode,  carbon  and  a  small 
quantity  of  a  gas  the  nature  of  which  could  not  be 
established.  Bourgoin,3  on  electrolyzing  the  dilute 


1  Tommasi,  TraitS  d'Electrochimie,  724;  Comp.  rend.,  69,  1374; 
ibid.,  70,  731;  Chem.  Ber.,  29,  1390. 
*  Neue  Peters.  Acad.  Bull.,  4,  81. 
3  Ann.  chim.  phys.,  [4],  14,  157. 


OF  ALIPHATIC  COMPOUNDS.  15 

acid,  observed  hydrogen  at  the  negative  pole  and 
oxygen,  carbon  dioxide,  and  traces  of  carbon  mon- 
oxide at  the  positive  pole. 

The  reactions  involved  in  the  decomposition  of  the 
alkali  salts  are  more  interesting.  Kolbe,1  on  decom- 
posing a  concentrated  solution  of  potassium  acetate, 
obtained  a  hydrocarbon  in  addition  to  other  decom- 
position products.  According  to  the  idea  then  pre- 
vailing acetic  acid  underwent  oxidation  in  the  sense 
that  it  was  thereby  changed  into  carbon  dioxide  and 
methyl,  both  of  which  appeared  at  the  positive  pole, 
while  at  the  negative  pole  only  hydrogen  was  evolved, 
and  a  part  of  the  methyl  was  oxidized  to  methyl 
oxide.  The  hydrocarbon  evolved  was  in  fact  ethane, 
which  always  accompanies  the  decomposition  of  potas- 
sium acetate  solutions,  while  the  other  decomposition 
products  formed  vary  with  the  density  of  the  electric 
current  and  the  temperature  of  the  solutions.  Thus 
Kolbe  identified  methyl  ether  and  methyl  acetate  in 
the  solution,  while  Bourgoin  observed  no  decomposi- 
tion products  other  than  carbon  monoxide  and 
dioxide.  Jahn,a  who  employed  currents  of  very  low 
electrode  density,  obtained  by  the  electrolysis  of  an 
almost  saturated  solution  of  sodium  acetate  only  car- 
bon dioxide,  ethane,  and  hydrogen.  The  formation 


1  Lieb.  Ann.,  69,  279. 

*  Grundriss  d.  Elektrochemie,  1895,  p.  292. 


1  6       ELECTROLYSIS  AND   ELECTROSYNTHESIS 

of  ethane  can  be  explained   by  assuming  either  the 
direct  oxidation  of  the  acetic  acid, 


or  the  decomposition  of  the  anion, 

CH3COO\  _  c  H  4-  2CO 
CH8COO/-    ^""t        U'' 

K£kule  l  advanced  a  theory  based  on  the  phenom- 
ena of  decomposition,  and  from  this  deduced  certain 
formulae  which  make  i*  possible  to  predict  the  nature 
of  the  products  resulting  from  the  electrolysis  of 
monobasic  and  dibasic  acids  of  the  fatty  acid  series. 

Since,  however,  the  reaction  is  influenced  by  the 
slightest  variation  of  conditions,  his  formulae  hold 
good  only  in  the  case  of  the  decomposition  of  per- 
fectly pure  substances,  a  condition  seldom  met  in 
practice. 

Lob  a  is  in  favor  of  accepting  the  theory  advanced 
by  Kekule,  who  in  the  case  of  phthalic  and  acetic 
acids  sought  by  experiment  to  prove  the  intermediate 
formation  of  the  anhydride,  while  Schall  8  assumes  the 
formation  of  an  acid  superoxide: 

R.COO  --  h  R.COO—  =  R.COO\ 

R.COO/ 

R.COO\      ^  TJ  ,  -m 
R.COO/  =  °a' 

1  Lieb.  Ann.,  131,  79. 

8  Ztschr.  f.  Elektrochemie,  3,  42. 

3  Ztschr.  f.  Elektrochemie,  3,  83.    . 


OF  A  LIP  HA  TIC  COMPO  UNDS.  1 7 

This  conclusion  is  drawn  from  the  observed  fact 
that  the  dithionic  acids  upon  the  electrolysis  of  their 
alkali  salts  give  acid  supersulphides  which  correspond 
with  the  superoxides: 

R.CSS—  -L-  R.CSS—  =  R.CSS\  (  UNIVERSIT 

R'CSS/'V^u 

In  contrast  to  the  acid  superoxides,  the  acid  super- 
sulphides  are  stable  compounds. 

The  reactions  and  the  corresponding  electrolytic 
products  which  occur  in  the  electrolysis  of  the  alkali 
salts  of  the  fatty  acids  were  thoroughly  investigated 
by  Rohland,1  who  electrolyzed  the  alkali  salts  of 
capronic,  caprylic,  and  heptylic  acids. 

Potassium  Capronate  gave  normal  decane,  C,0HM; 

Potassium  Caprylate  analogously  gave  normal  tetra- 
decane,  CJ4H30;  while 

Potassium  Heptylate  gave  besides  dodecane,  C12H26, 
a  small  quantity  of  an  unsaturated  hydrocarbon, 
probably  octylene,  C8H18. 

The  fatty  acids  with  ethylene  bond  behave  differ- 
ently. In  their  case  no  smooth  reaction  occurs.  The 
electrolysis  of  undecylenic  acid,  for  example,  yielded  a 
mixture  of  several  unsaturated  hydrocarbons,  a  result 
similar  to  that  obtained  in  the  investigation  of  potas- 
sium oleate,  the  only  outcome  of  which  was  a  mixture 
of  various  compounds  which  could  not  be  separated. 

1  Ztschr.  f.  Elektrochemie,  4,  120. 


1 8       ELECTROLYSIS  AND   ELECTROS YN THESIS 

Kolbe  and  Kemp  *  obtained  by  the  electrolysis  of  a 
concentrated  potassium  acetate  solution,  at  the  anode, 
hydrogen,  methyl-acetic  ester,  methyl-formic  ester, 
ethane,  ethylene,  and  carbon  dioxide;  at  the  cathode, 
hydrogen  and  potassium  hydroxide.  In  an  alkaline 
solution  of  the  same  salt  Bourgoin'  obtained  a  mix- 
ture of  sodium  formate,  but  so  far  as  hydrocarbons 
were  concerned  could  only  prove  the  presence  of 
ethane  and  ethylene. 

Besides  the  alkali  salts,  the  copper,  lead,  man- 
ganese, and  uranium  salts  were  subjected  to  electroly- 
sis by  Dupre,3  Wiedemann,4  Despretz,6  and  Smith.6 
The  metals  were  precipitated  at  the  anode,  a  portion 
of  the  manganese  and  lead  in  the  form  of  superoxides. 

According  to  Bauer,7  in  the  electrolysis  of  the 
acetic  acid  salts  of  metals  possessing  a  constant 
valence  (K,  Na,  NH4,  Mg,  Ca,  Zn,  and  Al),  when 
cold,  moderately  dilute  solutions  and  relatively  high 
current  densities  are  employed,  gases  consisting  chiefly 
of  ethane  and  carbon  dioxide  are  given  off  at  the 
anode.  No  inconsiderable  quantities  of  ethylene  are 
formed  in  the  case  of  calcium,  magnesium,  and  potas- 


1  Journ.  prakt.  Chemie,  [2]  4,  46. 
8  Ann.  chim.  phys.,  [4]  14,  157. 
8  Archiv.  ph.  nat.,  35,  998. 

4  Pogg.  Ann.,  104,  162. 

5  Comp.  rend.,  45,  449. 

6  Chem.  Ber.,  13,  151. 

1  Dissert.  Giessen,  1897;  Wied.  Beibl.,  21,  601. 


OF  ALIPHATIC  COMPOUNDS.  1 9 

sium  acetate  solutions.  Very  small  amounts  on  the 
contrary  result  from  the  electrolysis  of  the  sodium, 
ammonium,  and  zinc  salts.  At  the  boiling  tempera- 
ture the  gases  consist  mostly  of  oxygen  and  contain 
in  addition  a  little  carbon  dioxide  and  a  very  small 
quantity  of  ethane.  Metals  with  several  valences 
change  to  the  higher  valence. 

Monochlor-acetic  Acid,  according  to  Kolbe,1  breaks 
up  on  electrolysis  into  hydrochloric  and  acetic  acids, 
as  a  result  of  the  action  of  the  electrolytic  hydrogen : 

CHSC1.COOH  +  2H  =  CH8COOH  +  HC1. 

Trichlor-acetic  Acid  gives  the  same  products  and 
in  addition  also,  according  to  Elbs,  tri-chlor-methyl 
ester,  CC1,.CO3.CC13. 

Cyan-acetic  Acid. — Moore3  obtained  at  the  positive 
pole  carbon  dioxide  besides  traces  of  nitrogen,  and 
ethylene  cyanide ;  at  the  negative  pole  hydrogen  and 
potassium  hydroxide,  bodies  analogous  to  the  decom- 
position products  of  sodium  acetate. 

Thio-acetic  Acid." — This  compound  gives  acetyl 
disulphide.5  The  acid  is  formed  at  the  positive  pole 
if  a  solution  of  pure  acetic  acid  which  has  been  sat- 
urated with  hydrogen  sulphide  is  subjected  to  elec- 

1  Tommasi,  Trait6  d'Electrochimie,  1889,  p.  750. 

2  Journ.  prakt.  Chemie,  [2]  47,  1104;  ibid.,  [2]  55,  502. 
8  Chem.  Ber.,  4,  519. 

4  Zeitschr.  f.  Elektroch.,  3,  42. 
6  Chem,  Ber.,  3,  297. 


2O       ELECTROLYSIS  AND   ELECTROS YNTKESIS 

trolysis  and  a  slow  current  of  the  gas  is  conducted 
through  the  solution  during  the  operation. 

Propionic  Acid. — The  electrolysis  of  a  concentrated 
solution  of  sodium  propionate  was  carried  out  by 
Jahn  1  and  yielded,  when  the  density  of  the  currents 
employed  was  not  too  great,  hydrogen,  ethylene,  and 
carbon  dioxide,  but  no  butane. 

Butyric  Acid. — The  two  butyric  acids  were  elec- 
trolyzed  by  Bunge.2  With  isobutyric  acid  it  was 
not  possible  to  obtain  hexane,  but  the  normal  acid 
yielded  some  butane  besides  larger  quantities  of 
propylene. 

The  great  influence  of  concentration,  current  den- 
sity, and  especially  of  temperature  is  again  empha- 
sized in  the  researches  of  Bunge.  The  various 
conditions  which  were  followed  by  the  individual  in- 
vestigators explain  sufficiently  the  frequent  differences 
occurring  in  the  results.  The  repetition  of  an  elec- 
trolytic experiment  is  only  possible  when  an  exact 
statement  of  all  the  factors  is  given.  This  require- 
ment is,  however,  entirely  omitted  in  the  published 
experiments  above  mentioned. 

Careful  and  reliable  investigations  on  the  electroly- 
sis of  the  potassium  salts  of  butyric  and  isobutyric 
acids  have  been  published  by  M.  F.  Hamonet.3  His 


1  Grund.  d.  Elektroch.,  1895,  293. 

8  Journ.  d.  russ.  phys.  Gesellsch.,  I,  525. 

3  Comp.  rend.,  123,  252. 


OF  ALIPHATIC  COMPOUNDS.  21 

apparatus  consisted  of  a  copper  beaker  23  cm.  high 
and  8  cm.  in  diameter,  which  served  as  the  cathode. 
A  porous  earthenware  cell,  which  contained  the  anode 
and  was  closed  with  a  three-hole  stopper,  stood  in  the 
beaker.  Through  the  perforations  of  the  stopper 
passed  a  thermometer,  a  gas-conducting  tube,  and  the 
electric  conductor  leading  to  the  anode.  The  anode 
used  in  some  experiments  was  a  platinum  wire  i  mm. 
in  diameter  and  2  m.  in  length,  in  others  a  platinum 
cylinder  14  cm.  high  and  2.5  cm.  in  diameter.  This 
variation  of  current  density  was,  however,  of  second- 
ary importance.  Solutions  of  the  potassium  salts 
having  a  specific  gravity  of  1.08-1.12  were  used  as 
the  electrolyte.  Current  strengths  of  4-5  amperes 
were  reached  with  a  difference  of  potential  at  the  poles 
of  6-8  volts.  The  electrolysis  was  continued  2-3 
hours,  the  solution  being  kept  cool.  The  following 
results  were  obtained : 
Potassium  Butyrate, 

CH8.CH,.CH2.COOK. 

225  g.  propylene  bromide  (CH3.CHBr.CH2Br),  corre- 
sponding to  47  g.  propylene  (CH2  —  CH  =  CH2); 
1 8  g.  isopropyl  alcohol  (CH,.CHOH.CH3);  4.5  g. 
butyric  isopropyl  ester  (CH3.CH3.CH3.COOCH(CH8)a); 
4.5  g.  complicated  products,  which  became  resinous 
when  the  ester  was  saponified  by  boiling  with  alkali 
hydroxide. 


22       ELECTROLYSIS  AND   ELECTROS 'YN  THESIS 

Hexane  (CH3.CH2.CH2.CHa.CH2.CH3)  and  propyl 
alcohol  (CH3.CHa.CHaOH)  could  not  be  detected. 
They  could,  therefore,  only  have  been  formed  in 
extremely  small  quantities.  The  very  remarkable 
formation  of  isopropyl  alcohol  can  only  be  explained 
by  assuming  the  hydration  of  propylene  or  the  molec- 
ular rearrangement  of  the  group  CH8.CH,.CHa — . 

Potassium  Isobutyrate, 

(CH9)a:CH.COOK. 

This  salt  gave  300  g.  propylene  bromide  (CH,. 
CHBr.CHaBr),  equivalent  to  62  g.  propylene  (CH3. 
CH:CHa);20  g.  isopropyl  alcohol  ((CH3)a:CHOH); 
over  12  g.  isobutyric  isopropyl  ester, 

((CH,),:  CH.COOCH(CH8)a); 

6  g.  of  an  oil  having  a  pepper-like  odor  and  boiling  at 
130-160°. 

In  this  case  also  the  paraffine  isohexane  (CH3),:CH. 
CH  :(CH8)a  was  not  formed. 

Hamonet  draws  the  following  conclusions  from 
these  results: 

I.   The  equation 

2C.HM+l.COO-=  C.H4K+2+  2CO., 

representing  the  reaction  in  the  electrolysis  of  the 
alkali  salts  of  the  fatty  acids,  which  since  the  experi- 


OF  ALIPHATIC  COMPOUNDS.  2$ 

ments  of  Kolbe  has  been  almost  universally  accepted, 
can  no  longer  claim  to  represent  the  true  fact  in  the 
case,  since  no  or  almost  no  paraffines  result  from  this 
operation. 

2.  The  olefine  CMH2W  sometimes  predominates 
among  the  products  formed  by  the  electrolysis  of  the 
alkali  salts  of  the  fatty  acids, 


The  general  nature  of  the  reactions  is  represented 
by  the  following  equation  : 

2C,H1,  +  I.COO—  =  C.H-  +  1.COOH  +  C.HM+  CO.. 

3.  An  alcohol  with  n  carbon  atoms  is  always  formed 
if  the  acid  contains  (n  +  i)  carbon  atoms.  The  struc- 
ture of  the  alcohol  is  not  always  that  which  is 
expected.  Frequently  more  than  a  third  of  the 
energy  of  the  current  is  expended  in  the  formation  of 
the  alcohol.  Whether  the  alcohol  is  generated  by 
the  saponification  of  the  ester  present,  according  to 
the  equation 

2C»H2B  +  ,COO-  =  C.HM  +  I.COOC.H,.+1  +  CO,, 

or  whether  it  is  formed  by  the  hydration  of  the 
defines,  C,H1(I  +  H2O  =  CwHaM+1OH,  is  still  uncer- 
tain. 

To  decide  this  question  a  more  thorough  investiga- 
tion of  the  substances  resulting  from  the  electrolysis 


24       ELECTROLYSIS  AND   ELECTROS YNTHESIS 

of  compounds  possessing  higher  molecular  weights  is 
required. 

Valeric  Acid.— Kolbe1  electrolyzed  the  potassium 
salt  and  obtained  as  the  chief  product  octane  (di- 
isobutane), 

£[J'\CH.CH,.CH..CH/[:{*. 

Besides  this  there  appeared  as  decomposition  prod- 
ucts water,  carbonic  acid  gas,  butylene,  and  the 
butyl  ester  of  valeric  acid. 

Brester,"  who  performed  his  experiments  under 
different  conditions,  obtained  at  the  anode  a  gaseous 
mixture  of  carbon  dioxide,  butylene,  and  oxygen. 

Capronic  Acid.  —  A  concentrated  solution  of  the 
potassium  salt  gave  decane  and  traces  of  the  amyl 
ester  of  capronic  acid,  both  of  which  are  normal 
decomposition  products.  The  electrolyses  were  made 
by  Brazier  and  Gossleth,3  by  Wurz,4  and  by  Rohland. 

(Enanthylic  Acid. — The  normal  acid  was  electro- 
lyzed by  Brazier  and  Gossleth 6,  under  conditions 
similar  to  those  for  capronic  acid,  and  gave  two 
hydrocarbons,  CiaH26  and*  CnH24,  in  addition  to 
hydrogen,  potassium  carbonate  and  acid  potassium 
carbonate. 

1  Lieb.  Ann.,  69,  257. 

*  Jahresber.  f.  Chem.,  1859,  P-  86;  ibid.,  1866,  p.  87. 
»  Tommasi,  Traite  d'Electroch.,  1889,  p.  757. 
4  Ibid.  6  Ibid. 


OF  ALIPHATIC  COMPOUNDS.  2$ 

Oxalic  Acid. — The  deportment  of  the  saturated  solu- 
tion of  the  free  acid  on  electrolysis  was  determined 
by  Brester,1  Bourgoin,2  Balbiano  and  Alessi,3  Bunge,4 
and  Renard.6  The  general  result  was  that  oxygen 
and  carbon  dioxide  were  obtained  at  the  anode  and 
hydrogen  at  the  cathode.  It  is  possible  to  completely 
oxidize  oxalic  acid  to  carbon  dioxide.  On  this  prop- 
erty depends  the  great  importance  of  oxalic  acid  in 
quantitative  electrolytic  analysis,  into  which  it  has 
been  introduced  by  Classen.8 

The  ability  of  ammonium  oxalate  to  form  soluble 
double  salts  with  many  difficultly  soluble  or  insoluble 
metallic  salts  is  in  accord  with  the  favorable  conduct 
of  the  acid  on  electrolysis,  by  which  operation  it  may 
be  entirely  removed  from  the  solution  in  the  form  of 
gas.  The  reducing  effects  of  the  current  on  oxalic 
acid  were  also  observed.  Thus  on  electrolyzing  both 
the  free  acid  and  its  sodium  salt  Balbiano  and  Alessi 
were  able  to  prove  the  presence  of  glycolic  acid. 

The  oxidation  is  not  complete  if  the  electrolysis  is 
conducted  in  the  cold  solution,  carbon  monoxide 
as  well  as  carbon  dioxide  being  then  formed  at  the 
positive  pole. 

1  Jahresber.  f.  Chemie,  1866,  p.  87. 
8  Comp.  rend.,  67,  97. 

3  Gazz.  chim.,  1882,  p.  190;  Chem.  Ber.,  15,  2236. 

4  Chem.  Ber.,  9,  78. 

5  Ann.  chim.  phys.,  [5]  17,  289. 

8  Classen,  Quan.  Analysis  by  Electrolysis  (Wiley  &  Sons,  N.  Y.). 


26       ELECTROLYSIS  AND   ELECTROS YNTHESIS 

The  decomposition  reactions  of  oxalic  acid  salts  are 
entirely  analogous  to  those  of  the  free  acid.  In  alka- 
line solution  the  oxidation  proceeds  more  rapidly  than 
in  neutral  solution  because  of  the  better  conductivity 
of  the  alkalies. 

Malonic  Acid. — This  acid  was  investigated  by  Bour- 
goin.1  In  a  concentrated  solution  of  sirupy  consis- 
tency it,  like  oxalic  acid,  is  only  slowly  oxidized  to 
carbon  dioxide,  with  the  evolution  of  hydrogen.  A 
strongly  concentrated  solution  of  the  unaltered  acid  is 
found  surrounding  the  positive  electrode,  even  after 
an  electrolysis  of  long  duration.  On  the  electrolysis 
of  the  sodium  salt  carbon  monoxide  is  also  present  in 
the  escaping  gas  mixture.  The  ratio  of  the  different 
gases,  carbon  dioxide,  carbon  monoxide,  and  oxygen, 
remains  fairly  constant  during  the  period  of  electroly- 
sis (85.8$,  9.7*,  4.5*). 

In  alkaline  solution  the  decomposition  products  are 
the  same  as  in  neutral  solution,  the  ratio  only  of  the 
separate  gases  being  different,  and  varying  with  the 
duration  of  the  electrolysis. 

Succinic  Acid. — Bourgoin2  and  Kekule3  found  that 
the  free  acid  underwent  oxidation  with  difficulty,  only 
a  small  quantity  of  carbon  monoxide  in  addition  to 
some  oxygen  and  carbon  dioxide  being  formed. 

1  Ann.  chim.  phys.,  [i]  14,  157;  Comp.  rend.,  90,  608. 
8  Bull.  soc.  chim.,  [2]  9,  301;  ibid.,  21,  1695. 
3  Lieb.  Ann.,  131,  84. 


OF  ALIPHATIC  COMPOUNDS.  2J 

The  neutral  sodium  salt  gave  the  same  products,  as 
did  also  the  alkaline  solution  of  this  salt,  except  that 
in  the  latter  experiment  the  formation  of  carbon 
monoxide  predominated.  If,  however,  four  molecular 
equivalents  of  sodium  succinate  were  treated  with  one 
equivalent  of  sodium  hydroxide,  ethylene  and  a  little 
acetylene  could  also  be  detected.  Kolbe  1  states  that 
methyl  oxide  is  also  formed ;  Bourgoin,  however,  was 
unable  to  confirm  this  statement. 

Glutaric  Acid.  —  The  results  which  Reboul  and 
Bourgoin2  obtained  with  this  acid  are  the  following: 

The  greater  part  of  the  acid  remains  unchanged, 
while  a  small  part  only  is  decomposed  according  to 
the  equation 

C.H.O.  +  70  =  2CO,  +  3CO  +  4H.O. 


A  hydrocarbon  of  the  composition 


was  not  formed. 

Similar  observations  were  made  in  the  electrolysis 
of  potassium  glutarate,  likewise  in  alkaline  solution. 

Pyrotartaric  Acid. — The  investigators  just  men- 
tioned, on  electrolyzing  a  solution  of  the  neutral 
potassium  salt,  observed  the  immediate  precipitation 

1  Lieb.  Ann.,  113,  244. 
1  Comp.  rend.,  84,  1231. 


28       ELECTROLYSIS  AND   ELECTROS 'YN  THESIS 

of  the  acid  salt.  (Different  behavior  from  glutaric 
acid,  in  the  case  of  which  the  formation  of  the  acid 
salt  does  not  take  place.)  After  a  time  the  crystals 
disapppear,  the  free  acid  being  regenerated.  In 
alkaline  solution  also,  the  formation  of  the  acid  salt 
occurs,  after  a  longer  period  of  electrolysis.  Never- 
theless the  continuous,  though  limited,  evolution  of 
carbon  dioxide  and  carbon  monoxide  is  a  proof  of 
partial  oxidation. 

Itaconic  Acid. — The  concentrated  solution  of  the 
alkali  salt  electrolyzed  by  Aarland  1  gave  a  hydrocar- 
bon isomeric  with  allylene,  C3H4,  which  is  said  to 
have  the  formula  CH2  =  C  =  CH2.  Along  with  this 
compound,  some  propylene  was  formed,  while  a  por- 
tion of  the  acid  was  always  regenerated. 

Citraconic  Acid.3 — The  concentrated  solution  of  the 
sodium  salt,  likewise  electrolyzed  by  Aarland,  yielded, 
besides  a  hydrocarbon,  C3H4,  small  traces  of  acrylic 
and  mesaconic  acid. 

Mesaconic  Acid,  under  the  same  conditions,  gives 
the  same  hydrocarbon  and  traces  of  acrylic  and 
itaconic  acid. 

Malic  Acid. — The  electrolysis  of  malic  acid  was  per- 
formed by  Bourgoin*  and  Brester.4  The  free  acid, 

1  Journ.  prakt.  Chem.,  [2]  6,  256. 

2  Journ.  prakt.  Chem.,  J,  142. 
8  Bull.  soc.  chim.,  [2]  9,  427. 
4Jahresb.  f.  Chem.,  1866,  p.  87. 


OF  ALIPHATIC  COMPOUNDS.  2$ 

which  is  only  slowly  decomposed,  and  the  neutral 
alkali  salt  both  gave  the  same  products,  carbon 
dioxide  and  a  little  carbon  monoxide  and  oxygen. 
After  the  completion  of  the  experiment  the  solution 
contained  some  aldehyde  and  acetic  acid. 

Tartaric  Acid  (Dextrorotary). — For  our  knowledge 
of  the  deportment  of  this  acid  on  electrolysis  we  are 
also  indebted  to  Bourgoin.1  The  free  acid  is  partially 
oxidized  to  carbon  dioxide  and  carbon  monoxide, 
while  the  solution  contains  acetic  acid.  Neutral 
potassium  tartrate  gives  principally  carbon  dioxide 
besides  a  little  carbon  monoxide  and  oxygen,  acid 
potassium  tartrate  being  at  the  same  time  deposited. 
In  alkaline  solutions  the  gases  carry  with  them  traces 
of  ethane,  the  formation  of  which  is  due  to  potassium 
acetate  which  is  found  present  in  the  solution  at  the 
end  of  the  operation. 

Before  proceeding  to  a  discussion  of  the  acids  still 
to  be  considered,  the  deductions  which  Bourgoin3 
draws  from  his  numerous  experiments  will  be  men- 
tioned briefly.  He  regards  the  intermediate  formation 
of  the  anhydride  as  the  most  important  process  in  the 
electrolysis  of  organic  acids,  since  by  the  splitting  off 
of  oxygen  this  produces  secondary  oxidation  products. 
He  considers,  moreover,  the  transformation  of  the 
acid  anhydride  into  the  hydrate,  by  the  addition  of 

1  Comp.  rend.,  65,  1144. 

1  Annal.  chim.  phys.,  [4],  14,  157. 


3O       ELECTROLYSIS  AND   ELECTROSYNTHESIS 

water,  and  the  oxidation  of  the  acids  by  oxygen 
formed  from  the  acid  itself  as  belonging  to  the 
secondary  processes.  This  explanation  coincides  with 
the  fact  that  water  is  not  an  electrolyte,  or  at  least 
only  a  poor  one,  and  acts  chiefly  as  a  dissociation 
medium.  The  typical  reactions  in  the  electrolysis  of 
acetic  acid  are,  for  instance,  the  following: 
Electrolytic  decomposition, 


2CHS.COOK  =  >  -  o  +  Q     +  K,. 

Characteristic  oxidation, 


A  too  strict  adherence  to  the  chemical  arrangement 
is  not  conducive  to  clearness.  After  mentioning  the 
investigations  of  Kekule,1  the  later  experiments  of 
Miller  and  Hofer,  Brown  and  Walker,  etc.,  will  be 
discussed  in  this  connection. 

Kekul£  '  investigated  the  electrolysis  of  maleic  acid 
and  brom-maleic  acid.  The  former  gave  acetylene, 
besides  a  small  quantity  of  succinic  and  fumaric  acid; 
the  latter,  on  the  contrary,  gave  only  hydrobromic 
acid  and  carbon  monoxide.  Like  malic  acid,  fumaric 
acidj  at  the  beginning  of  the  experiment,  gave  only 
pure  acetylene,  but  after  the  operation  had  continued 

1  Lieb.  Ann.,  131,  79. 


OF  ALIPHATIC   COMPOUNDS.  31 

for  some  time  the  acetylene  was  found  to  be  mixed 
with  oxygen. 


EXPERIMENTS  OF  MILLER  AND  HoFER.1 

I.  The  investigations  carried  out  by  Miller  and 
Hofer  are  improvements  over  those  previously  made, 
since  they  give  a  much  clearer  insight  into  the  process 
of  the  decomposition.  In  the  method  which  was 
employed,  namely,  that  of  allowing  the  solutions  to 
slowly  flow  over  the  electrodes,  the  compounds  first 
formed  were  removed  from  the  region  of  electrolytic 
action. 

In  this  way  it  was  possible  to  isolate  certain  sub- 
stances which  would  otherwise  have  undergone 
secondary  decomposition.  In  the  researches  cited 
below,  however,  accurate  data  concerning  current 
relations  are  lacking.  Classen3  has  accurately  ex- 
plained what  data  are  necessary  for  repeating  an  elec- 
trolytic experiment. 

Glycolic  Acid. — The  concentrated  solution  of  the 
sodium  salt  yielded  at  the  positive  pole  formaldehyde 
in  large  quantities  and  some  formic  acid,  the  latter 
breaking  up  from  the  action  of  the  current  into  carbon 
monoxide  and  dioxide. 


1  Chem.  Ber.,  27,  461. 

*  Classen,  "  Quan.  Analysis  by  Electrolysis,"  page  23. 


32       ELECTROLYSIS  AND   ELECTROS YN THESIS 

Ordinary  Lactic  Acid. — As  Kolbe  '  had  already  dis- 
covered, the  concentrated  solution  of  the  potassium 
salt  gave  carbon  dioxide  and  acetic  aldehyde.  The 
investigators  above  mentioned  also  remarked  the 
presence  of  some  formic  acid.  When  the  solution 
about  the  positive  pole  was  kept  slightly  alkaline, 
aldol  and  crotonic  aldehyde  were  formed  instead  of 
acetic  aldehyde. 

Sarco-lactic  Acid. — When  the  solution  surrounding 
the  positive  pole  was  kept  neutral  a  concentrated 
solution  of  the  sodium  salt  yielded  acetic  aldehyde 
and  carbon  dioxide. 

^-Oxy-butyric  Acid. — This  substance  was  converted 
into  carbon  dioxide,  propionic  aldehyde,  and  formic 
acid. 

<*-Oxy-isobutyric  Acid. — This  compound  gave  car- 
bon dioxide,  carbon  monoxide,  and  acetone. 

Tartaric  Acid. — From  the  electrolysis  of  a  concen- 
trated solution  of  potassium  tartrate,  carbon  dioxide, 
carbon  monoxide,  oxygen,  a  little  formic  aldehyde, 
and  some  formic  acid  were  obtained,  but  no  acetic 
acid  and  ethylene,  as  stated  by  Bourgoin. 

Hydracrylic  Acid. — Resin  and  a  little  formic  acid 
were  found  present  in  the  electrolyte  about  the  posi- 
tive pole. 

/?-Oxy-butyric  Acid. — From  this  acid  were  obtained 
carbon  monoxide,  carbon  dioxide,  crotonic  aldehyde, 

1  Lieb.  Ann.,  113,  214. 


OF  ALIPHATIC  COMPOUNDS.  33 

a  little  formic  acid,  a  resin,  and  a  number  of  unsatu- 
rated  hydrocarbons  which  were  not  further  investi- 
gated. 

Phenyl-/?-lactic  Acid. — The  solution  after  electroly- 
sis contained  benzaldehyde,  besides  resinous  bodies. 

Methyl-glycolic  Acid. — The  solution  of  this  acid 
after  electrolysis  contained  formic  aldehyde,  formic 
acid,  and  possibly  methyl  alcohol.  Oxygen,  carbon 
monoxide,  and  carbon  dioxide  were  evolved. 

Mandelic  Acid. — The  electrolysis  of  this  acid  re- 
sulted in  the  formation  of  benzaldehyde  and  the 
gases  mentioned  above. 

Glyceric  Acid. — Like  mandelic  acid,  glyceric  acid 
was  decomposed  into  carbon  monoxide,  carbon  diox- 
ide, and  oxygen,  formic  aldehyde  and  formic  acid 
being  found  in  the  solution. 

Phenyl-glyceric  Acid. — The  products  resulting  from 
the  electrolysis  of  this  acid  were  the  same  as  those 
obtained  from  mandelic  acid. 

Malic  Acid. — This  compound  yielded  carbon  diox- 
ide, oxygen,  carbon  monoxide,  acetic  aldehyde,  and 
crotonic  aldehyde. 

Racemic  Acid. — On  the  electrolysis  of  this  acid  the 
gases  given  above  were  obtained  and  also  an  aldehyde 
which  was  not  further  investigated. 

Ethyl-tartaric  Acid. — This  gave  the  same  gases,  but 
any  other  gases  which  may  have  been  formed  were 
not  identified. 


34       ELECTROLYSIS  AND    ELECTROS YNTHESIS 

2.  Electrosyntheses. — The  same  investigators  re- 
cently 1  added  to  our  knowledge  on  this  subject  by 
submitting  to  electrolysis  solutions  containing  the 
potassium  salts  of  mono-basic  acids  and  the  ethyl 
esters  of  the  mono-potassium  salts  of  dibasic  acids  dis- 
solved in  equi-molecular  proportion.  This  was  in 
accordance  with  the  experiments  made  by  Brown  and 
Walker. 

In  this  way  they  prepared  butyric  ethyl  ester  from 
potassium  acetate  and  potassium- ethyl  succinate.  The 
synthesis  of  the  ethyl  ester  of  valeric,  capronic,  and 
isobutyl-acetic  acid  was  also  effected. 

The  reactions  all  take  place  according  to  the  follow- 
ing equation: 
XCOOK  +  COOKY.COOC2H5 

=  K2  +  2CO,  +  XY.COOCaH5. 

In  accordance  with  a  similar  principle  they  obtained 
ethyl  alcohol  from  potassium  acetate  and  potassium 
glycolate.  If  potassium-ethyl  malonate  was  taken  as 
one  of  the  salts  and  a  solution  of  this  with  potassium 
acetate,  propionate,  or  butyrate  was  electrolyzed  there 
was  formed  the  ethyl  ester  of  propionic,  butyric,  or 
valeric  acid,  respectively. 

v.  Miller"  applied  this  method  to  a  number  of 
other  mixtures.  Thus  upon  the  electrolysis  of  a  mix- 
ture of  acetic  ester  with  tricar  bally  lie  ester,  one  third 

1  Chem.  Ber.,  28,  2427;  Zeitschr.  f.  Elektroch.,  4,  55. 
3  Ztschr.  f.  Elektroch.,  4,  55. 


OF  ALIPHATIC   COMPOUNDS.  35 

of  which  was  saponified,  there  was  formed  principally 
ethyl-succinic  ester.  If  aromatic  ester  acids  were 
electrolyzed  with  potassium  acetate  a  similar  synthesis 
occurred. 

By  this  method  a-niethyl-hydrocinnamic  ester, 

C6H6  -  CH2  -  CH  -  COOC3H6, 

CH 

was  prepared  from  potassium-ethyl  benzyl-malonate  and 
potassium  acetate.  Dibenzyl-succinic  ester  is  formed 
at  the  same  time,  according  to  the  reaction  of 
C.  Brown : 

C6HB  -  CH2  -  CH  -  COOC2H6 
C6H5  -  CH,  -  CH  -  COOC2H6. 
This   reaction   does    not    take    place    if    potassium 
acetate  is  not  present. 

If  the  deportment  of  the  alkali  salts  of  the  mono- 
basic oxyacids  upon  electrolysis  is  analogous  to  that  of 
sodium  acetate  the  chief  products  to  be  expected  are 
symmetrical  glycols: 

2CnHro(OH)COO  -  =  CMHW(OH),  +  2CO,. 
According  to  Walker's1  experiments  this  is  not 
generally  the  case.  From  the  potassium  salt  of 
mandelic  acid  the  expected  product,  i.e.,  a  mixture 
of  hydrobenzoin  and  isohydrobenzo'in,  is  formed  only  in 
small  quantities;  benzaldehyde,  however,  is  formed 
in  larger  quantities. 

1  Journ.  Chem.  Soc.,  45,  1278, 


36       ELECTROLYSIS  AND   ELECTROS  YN  THESIS 

The  alkali  salts  of  oxyacids  give,  in  addition  to  the 
above,  many  other  substances,  principally  aldehydes, 
and  the  results  are  the  same  even  if  the  attempt  is 
made  to  weaken  the  action  of  the  electrolytic  oxygen 
by  converting  the  alcohols  into  esters. 

Thus  from  the  sodium  salt  of  glycolic  acid  (CH,OH. 
COOH),  ethyl-glycolic  acid  (CH.OC.H..COOH),  and 
a-lacttc  acM  (CH9.CH(OH)COOH)  the  chief  product 
obtained  is  acetic  aldehyde,  and  it  is  quite  possible  that 
the  production  of  hydrobenzom  and  isohydrobenzom 
from  mandelic  acid  is  due  to  the  electrolytic  reduction 
of  the  benzaldehyde  originally  formed. 

This  view  is  supported  by  the  investigations  of 
Kauffmann,1  who  actually  obtained  hydrobenzom  and 
isohydrobenzoin  by  the  direct  electrolytic  reduction 
of  benzaldehyde. 

Elbs3  emphasizes  the  fact  that  it  is  not  necessary 
to  suppose  that  aldehydes  are  a  result  of  secondary 
oxidation  produced  by  the  oxygen  available  in  the 
region  of  the  anode,  but  that  their  formation  can  also 
be  regarded  as  analogous  to  that  of  ethylene  from 
propionic  acid: 
2CH3.CHa.COO  -  =  CH3.CH2.COOH 


2CH3.CH(OH)COO  -  =  CH3.CH(OH).COOH 

CH3.CHO. 


1  Ztschr.  f.  Elektroch.,  2,  367. 
8  Jahrbuch.  d.  Elektroch.,  3,  295. 


OF  ALIPHATIC  COMPOUNDS.  37 

A  still  further  advance  in  this  field  is  the  successful 
substitution  of  iodine  and  of  nitro-groups  by  elec- 
trolysis. On  electrolyzing  propionic  acid  and  potas- 
ium  iodide  in  aqueous  solution  fi-iodo-propionic  acid 
was  formed,  due  to  the  int  i  rim  ill  ill  fgPjmtliii  1  1  of 


succmic  acid  :  OF  THE       r 

UNIVERSITY 


COOH.CH3.CHa.COOK  +  KI 

=  ICH2.CH2.COOH  +  2K  +  C02. 

Nitro-ethane  was  probably  obtained  in  small  quan- 
tities from  sodium  propionate  and  sodium  nitrite. 


ELECTROSYNTHESES  OF  BROWN  AND  WALKER.' 

A  systematic  synthesis  with  the  aid  of  the  electric 
current  was  first  attained  in  the  researches  of  Brown 
and  Walker.  Their  investigations  are  based  partly 
on  the  fact  observed  by  Kolbe  that  monobasic  fatty 
acids  yield  hydrocarbons,  and  partly  on  the  results  of 
the  experiments  of  Guthries,2  who  found  that  the 
ester  group  is  electrolytically  inactive.  These  facts 
justified  the  hypothesis  that  the  mono-esters  of 
dibasic  acids  would  behave,  under  the  action  of  the 
current,  like  monobasic  acids,  i.e.,  carbon  dioxide 


1  Lieb.  Ann.,  261,  107;  ibid.,  274,  41. 
?  Lieb.  Ann.,  99,  65. 


38       ELECTROLYSIS  AND   ELECTROSYNTHESIS 

would  be  split  off  and  esters  of  higher  dibasic  acids 
would  be  formed  according  to  the  equations 

2C,H6.OOC  -  CHa  -  COOK 

=C2H6.OOC-CHa-CHa-COOC2HB+2Ka+C02, 
2C2H6  -  OOC.CH3.CH2.COOK 

=CaH6.OOC.CH2.CHa.CH2.CHa.COOCaH6 


Their  experiments,  conducted  in  fairly  concentrated 
solutions  with  currents  of  high  density,  completely 
confirmed  this  supposition.  Under  these  conditions 
the  following  syntheses  were  made: 

I  .   Succinic  acid  from  ethyl-potassium  malonate. 

2.  Adipic  acid  from  ethyl-potassium  succinate. 

3.  Suberic  acid  from  ethyl-potassium  glutarate. 

4.  Sebacic   acid   from   the    ethyl-potassium   salt   of 
adipic  acid. 

5.  n-Dodecane-dicarboxylic   acid    from    the    ethyl- 
potassium  salt  of  suberic  acid. 

6.  n-Deca-hexane-dicarboxylic  acid  from  the  ethyl- 
potassium  salt  of  sebacic  acid. 

If  the  ethyl-potassium  salts  of  substituted  acids  are 
taken  as  a  starting-point  it  is  possible  to  obtain 
disubstituted  acids  according  to  the  above  reaction. 

1.  Ethyl-potassium  methyl-malonate  gave  the  two 
symmetrical  dimethyl-succinic  acids,  having  the  melt- 
ing-points 193°  and  121°. 

2.  Ethyl-pctassium  ethyl-malonate  gave   the   corre- 


OF  ALIPHATIC  COMPOUNDS.  39 

spending  symmetrical  diethyl-succinic  acids,  with  the 
melting-points  192°  and  130°. 

3.  Ethyl-potassium   dimethyl-malonate   gave    tetra- 

methyl-succinic  acid. 

4.  From    ethyl-potassium    diethyl-malonate   a   sub- 
stance of  the  composition  C14H2eO4,  which  differs  from 
the  expected   tetraethyl-succinic   acid  by  C2H4,    was 
obtained.     The  nature  of  this  body  has  not  yet  been 
determined. 

Hydrobromic  acid  splits  off  alcohol  the  compound 
CiaHaoO,,  which  has  perhaps  the  furfurane  formula 


(C2H&),:C-C:(CaH6),, 

i        i 
O  :  C      C  :  O 


being  formed. 

All  these  reactions  did  not  take  place  smoothly,  but 
were  accompanied  by  secondary  reactions,  principally 
oxidations,  which  were  limited  as  much  as  possible 
by  working  with  strong  concentrated  solutions  and 
low  temperatures.  Moreover,  the  formation  of  esters 
also  is  always  possible  according  to  the  equation 

2CH..COO  -  =  CH,COOCH,  +  CO3; 

and,  finally,  the  formation  of  unsaturated  esters  may 
take  place  as  illustrated  in  the  simplest  case: 


40       ELECTROLYSIS  AND   ELECTROS YN THESIS 

2C,H6COO  -  =  CaH4  +  CO,  +  C2HBCOOH, 
2C2H6OOC.CH2CH,.COO  -  =  2C2H5OOC.CH2 
-CH2.CH :  CH3+C2H6OOC.CH2.CH9.COOH+COa. 

In  this  way  it  was  possible  to  isolate  methyl-acrylic 
acid  by  the  electrolysis  of  ethyl-potassium  dimethyl- 
malonate,  and  ethyl-crotonic  acid  by  electrolyzing  a 
solution  of  the  ethyl-potassium  salt  of  diethyl-malonic 
acid.  On  the  electrolysis  of  sebacic  acid  the  ethyl 
ester  of  an  unsaturated  acid,  CH9:  CH(CH2)6.COOH, 
was  formed. 

Brown  and  Walker  1  also  electrolyzed  the  sodium- 
ethyl  salt  of  camphoric  acid  and  obtained  two  esters 
which  they  were  able  to  separate  by  means  of  frac- 
tional distillation.  One  of  these  (boiling-point  212- 
213°)  on  being  saponified  yielded  an  unsaturated 
monobasic  acid,  C9H14O2,  campholytic  acid ;  the  other, 
having  a  higher  boiling-point  (240-242°),  was  the 
neutral  ester  of  a  dibasic  acid,  C18H30O4,  to  which 
Walker  gave  the  name  of  camphothetic  acid.  The 
experiments  are  of  great  importance,  because  they 
prove  the  dibasic  nature  of  camphoric  acid,  a  fact 
which  is  doubted  by  Friedel. 

Walker  and  Henderson5  found,  moreover,  that 
upon  the  electrolysis  of  concentrated  aqueous  solu- 
tions of  the  potassium  salt  of  allocamphoric  ester  there 

1  Lieb.  Ann.,  274,  71. 

1  Journ.  Chem.  Soc.,  67,  337. 


OF  ALIPHATIC  COMPOUNDS.  4! 

are  formed  as  chief  products  the  ethyl  esters  of  a 
dibasic  acid,  C18Ha8(COOH)a,  and  of  a  monobasic  acid, 
C8H13COOH: 

/COOCaH6  __  ,        „  /COOCaH6. 


/COOCaH6  /COOCaH6 

2.  2U 


C8H13COOCaH5. 

It  has  been  found  on  further  investigation  l  that 
besides  the  strongly  dextrorotary  unsaturated  acid 
designated  as  allocampholytic  acid,  C8H13COOH,  an 
isomeric  acid  is  formed  which,  although  slightly 
dextrorotary  as  obtained,  is  perhaps  even  laevorotary 
in  an  entirely  pure  condition.  The  latter  on  being 
heated  to  200°  splits  off  carbon  dioxide  and  yields  a 
hydrocarbon,  C8H14,  which  boils  at  120-122°  and 
appears  to  be  identical  with  laurolene,  made  from 
camphoric  acid. 

A  ketonic  acid,  C8H3O.COOH,  melting-point  228°, 
is  also  found  as  an  additional  product  of  the  electroly- 
sis of  potassium  allocamphoric  ethyl  ester.  The 
authors  conclude  from  their  observations  that  cam- 
phoric acid  contains  the  group 
H 


H-C- 

1 

r/H 

|\COOH 

-  C-COOH. 

1 

Journ.  Chem.  Soc.,  69,  748. 


42       ELECTROLYSIS  AND   ELECTROS YNTHESIS 

It  is  expected  that  these  results  will  give  the  struc- 
tural formula  for  camphoric  acid. 

Following  the  experiments  of  Brown  and  Walker, 
Schields '  investigated  the  deportment  of  ethyl-potas- 
sium maleate  and  fumarate  on  electrolysis.  His 
results  confirm  the  experiments  of  Kekule.  During 
the  electrolysis  carbon  dioxide,  oxygen,  and  unsat- 
urated  hydrocarbons  were  evolved,  and  the  unchanged 
maleic  or  fumaric  acid  and  the  corresponding  ethyl 
esters,  respectively,  remained  in  the  solution. 

From  these  experiments  it  would  appear  that  un- 
saturated  acids  form  no  synthetic  products  on  elec- 
trolysis, and  the  aromatic  acids — phthalic  acid  and 
benzyl-malonic  acid — conduct  themselves  in  a  similar 
manner.  Finally  may  be  mentioned  the  electrolysis 
of  ethyl-potassium  oxalate,  which  yielded  ethylene  in 
addition  to  carbon  dioxide. 


ELECTROSYNTHESES  OF  MULLIKEN'  AND  WEEMS.S 

Mulliken  electrolyzed  the  sodium  compounds  of  the 
diethyl  esters  of  dibasic  acids  in  alcoholic  solution  and 
obtained  the  same  compounds  which  were  formed 
when  sodium  was  removed  by  iodine.  He  thus 
made: 

1  Lieb.  Ann.,  274,  64;  Journ.  Chem.  Soc.,  69,  737. 

2  Amer.  Chem.  Journ.,  15,  323. 
»  Ibid.,  1 6,  569. 


OF  ALIPHATIC  COMPOUNDS.  43 

1 .  Ethane-tetracarboxylic  ester  from  sodium-diethyl- 
ma Ionic  ester. 

2.  Ethane-hexacarboxylic  ester  from  sodium-met hane- 
tricarboxylic  ester. 

3.  Tetracetyl-ethane  from  acetyl-acetone. 

4.  A  thick  oil  which  contained  a  small  quantity  of 
diacetyl-succinic  ester  from  aceto-acetic  ester. 

The  conclusion  reached  by  Mulliken,  that  in  the 
electrolysis  of  certain  weak  organic  acids  a  portion  of 
the  anions  unite  in  pairs  without  undergoing  decom- 
position, was  closely  examined  by  Weems  as  to  its 
general  applicability  and  as  to  the  exact  nature  of  the 
chemical  changes  which  take  place.  All  direct 
attempts  to  oxidize  malonic  ester  with  hydrogen  per- 
oxide, potassium  permanganate,  and  chromic  acid,  and 
to  produce  an  effect  similar  to  that  caused  by  the 
current,  were  without  success. 

Weems,  on  electrolyzing  the  sodium  salt  of  methyl- 
malonic  ester  in  alcoholic  solution,  obtained  dimethyl- 
ethane-tetracarboxylic  ester;  ethyl-malonic  ester  yielded 
diethyl-ethane-tetracarboxylic  ester;  and  aceto-acetic 
ester  was  changed  to  diacetyl-succinic  ester. 

In  the  electrolysis  of  cyan-acetic  ester  the  formation 
of  dicyan-succinic  ester  could  not  be  observed;  like- 
wise a  union  of  the  anions  of  benzyl-malonic  ester, 
acetyl-malonic  ester,  and  acetyl-dicarboxylic  ester  did 
not  take  place.  Electrolysis  of  acid  amides  in  the 


44       ELECTROLYSIS  AND   ELECTROS 'YN THESIS 

form  of  their  sodium  or  mercury  compounds  yielded 
unchanged  amides. 

The  review  which  has  been  given  of  the  investiga- 
tions on  the  electrolysis  of  the  aliphatic  carboxylic 
acids  is  believed  to  include  all  present  information  on 
this  subject.  Of  the  investigations  mentioned,  an 
advance  is  shown  only  in  those  of  Kolbe-Bourgoin, 
Brown-Walker,  and  Mulliken-Weems.  The  action  of 
the  electric  current  has  been  used,  in  these  cases  at 
least,  for  effecting  a  limited  number  of  organic  syn- 
theses. A  number  of  papers  on  the  action  of  the 
electric  current  on  compounds  containing  cyanogen 
and  sulphur  will  next  be  mentioned. 

2.  Cyanogen  Compounds. 

Cyanogen. — Berthelot J  observed  that  cyanogen  was 
decomposed  into  its  elements  by  the  action  of  the 
electric  spark.  The  slightest  trace  of  water  in  the  gas 
caused  the  formation  of  hydrocyanic  acid  and  acety- 
lene. By  submitting  moist  cyanogen  gas  to  the 
action  of  the  voltaic  arc  Buff  and  Hofmann8  noted 
the  formation  of  carbon  dioxide,  carbon  monoxide, 
and  ammonia. 

Cyanogen  can  be  obtained  by  the  electrolysis  of  a 
solution  of  potassium  ferrocyanide.3 

1  Comp.  rend.,  82,  1360. 

*  Lieb.  Ann.,  113,  135. 

8  See  potassium  ferrocyanide.  p.  45. 


OF  ALIPHATIC  COMPOUNDS.  45 

Hydrocyanic  Acid.  —  Electrosynthesis  :  Berthelot l 
obtained  hydrocyanic  acid  by  passing  the  electric 
spark  through  a  mixture  of  acetylene  and  nitrogen. 
The  reaction  is,  however,  reversible.  On  allowing 
the  electric  spark  to  act  on  hydrocyanic-acid  gas  it 
was  decomposed  into  acetylene  and  nitrogen.  Hydro- 
cyanic acid  is  also  obtained  by  passing  the  electric 
spark  through  mixtures  of  ethylene  or  aniline  vapor 
with  nitrogen,  acetylene  with  nitric  oxide  (Hunting- 
ton  a),  nitrogen  with  benzol  (Perkin  3),  etc. 

Electrolysis:  In  sulphuric-acid  solution  hydro- 
cyanic acid  breaks  up  smoothly,  according  to  Gay- 
Lussac,4  into  hydrogen  and  cyanogen.  Concentrated 
hydrocyanic  acid  to  which  a  drop  of  sulphuric  acid 
has  been  added  gives  carbon  monoxide  and  ammonia 
(SchlagdenhaufTen  5). 

Potassium  Cyanide. — In  the  investigation  of  this 
salt,  conducted  by  the  author  last  mentioned,  it 
was  found  that  no  oxygen  escaped  at  the  anode, 
but  the  potassium  cyanide  was  oxidized  to  potassium 
cyanate. 

Potassium  Ferrocyanide. — This  compound  gives  at 
the  anode  hydrocyanic  acid  and  Prussian  blue  and  at 
the  cathode  hydrogen  and  potassium  hydroxide 

Bull.  soc.  chim.,  13,  107. 

English  patent,  14855;  German  patent,  93852. 

Jahresb.  f.  Chem.,  1870,  p.  399. 

Gilbert's  Ann.,  1811-1815;  Ann.  chim.  phys.,  78,  245. 

Jahresb.  f.  Chem.,  1863,  p.  305. 


46       ELECTROLYSIS  AND   ELECTROS 'YN  THESIS 

(Perrot1);    also    cyanogen,    according    to    Schlagden- 
hauffen.8 

Potassium  Ferricyanide  likewise  gives  on  electro- 
lysis Prussian  blue  at  the  anode. 

Sodio-nitro-prusside. — On  electrolyzing  a  dilute  solu- 
tion of  this  salt  for  a  prolonged  period  Weith  3  noted 
the  formation  of  ammonia  and  the  precipitation  of 
metallic  iron;  at  the  positive  electrode  Prussian  blue 
appeared,  and  nitrogen,  oxygen,  and,  if  the  operation 
was  long  continued,  nitric  oxide  also  were  given  off. 
In  a  concentrated  solution  much  ammonia  was  formed 
at  the  cathode  and  nitric  oxide  appeared  at  the  anode. 

Prussian  blue  can  also  be  obtained  according  to 
Luckow's  method  4  for  the  general  preparation  of  in- 
soluble compounds. 

Nitriles. — Ahrens,6  by  means  of  the  electrolytic 
addition  of  hydrogen,  succeeded  in  converting  nitriles 
into  primary  amines,  while  simultaneously  with  the 
reduction  a  partial  saponification  of  the  nitriles 
occurred,  as  represented  by  the  following  equation: 
R.CN  +  2H2O  =  R.COOH  +  NH,. 

Aceto-nitrile. — This  substance  yields  only  a  small 
quantity  of  ethylamine,  although  a  considerable 

1  Tommasi,  Traite  d'Electrochimie,  720. 
*  Jahresb.  f.  Chem.,  1863,  p.  305;  J.  prakt.  Chem.,  30,  145. 
1  Jahresb.  f.   Chem.,  1863,  p.  306;  ibid.,   1868,  p.  311;  Bull.  soc. 
chim.,  [2]  10,  I2i. 

4  German  patent,  91707. 

6  Ztschr.  f.  Elektroch.,  3,  99. 


Of   ALIPHATIC  COMPOUNDS.  47 

quantity  of  /z-propylamine  is  formed  from   n-propio- 
nitrite. 

The  reduction  of  aromatic  nitrites  takes  place  with- 
out the  occurrence  of  secondary  reactions.  This  is 
illustrated  in  the  formation  of  benzylamine  from 
benzo-nitrile  and  of  phenyl-ethylamine  from  benzyl- 
cyanide. 

3.  Compounds  Containing  Sulphur. 

Mercaptans. — Bunge  '  electrolyzed  the  alkali  salts  of 
mercaptans  and  observed  the  formation  of  disulphides 
at  the  positive  pole.  In  the  case  of  the  sulpho-com- 
pounds,  however,  the  free  acids  were  regenerated. 

Sodium-isethionate. — The  same  author  also  investi- 
gated sodium  isethionate,  but  could  note  the  formation 
of  only  the  free  acid  at  the  positive  pole. 

Methyl-sulphuric  Acid. — This  acid,  investigated  by 
Renard,3  yielded  hydrogen  at  the  negative  pole,  while 
formic  acid,  carbon  dioxide,  carbon  monoxide,  and 
trioxy-methylene,  besides  free  sulphuric  acid,  were 
found  present  at  the  positive  pole. 

Potassium  -  trichlor  -  methyl  Sulphate.  —  This  com- 
pound, electrolyzed  by  Bunge,8  gave  hydrogen  and 
alkali  at  the  negative  pole,  at  the  positive  pole 

1  Chem.  Ber.,  3,  911. 

8  Ann.  chim.  phys.,  [5]  17,  289;  Comp.  rend.,  90,  175,  531;  ibid., 
92,  965. 

*  Chem.  Ber.,  3,  911. 


48       ELECTROLYSIS  AND    ELECTROS  YN  THESIS 

oxygen,  carbonic-acid  gas,  chlorine,  sulphuric  acid, 
and  perchloric  acid. 

Potassium-trichlor-methyl  Sulphonate — This  salt  was 
electrolyzed  by  Kolbe  l  in  neutral  concentrated  aque- 
ous solution  and  gave  the  following  results: 

The  solution  became  strongly  acid  and  contained 
free  hydrochloric  and  sulphuric  acid.  Hydrogen  was 
gradually  evolved  at  the  negative  pole.  After  the 
decomposition  was  complete  the  solution  contained 
potassium  perchlorate,  which  was  also  observed  in  the 
case  of  potassium-trichlor-methyl  sulphate. 

Ethyl-sulphuric  Acid. — Ethyl-sulphuric  acid  gave, 
according  to  Renard,2  on  being  subjected  to  electroly- 
sis, at  the  negative  pole  hydrogen,  and  at  the  positive 
pole  acetic  acid,  some  formic  acid,  aldehyde,  and  sul- 
phuric acid.  In  concentrated  solution  a  greater  pro- 
portion of  acetic  acid  was  formed.  The  potassium 
salt  on  electrolysis  breaks  up,  according  to  Hittorf,3 
into  K  —  and  —  OSO2.OCaH6. 

Potassium-isoamyl  Sulphate,  according  to  Guthries, 
is  decomposed  into  oxygen,  valeric  acid,  and  sul- 
phuric acid. 

Potassium  Xanthate. — C.  Schall 4  obtained,  by  the 
electrolysis  of  potassium  xanthate  in  aqueous  solution, 
xanthogen  supersulphide,  as  might  be  expected: 

1  Journ.  prakt.  Chem.,  62,  311. 
*  Ann.  chim.  phys.,  [5]  17,  289. 
1  Pogg.  Ann.,  106,  530. 
4  Ztschr.  f.  Elektroch.,  2,  475. 


OF  ALIPHATIC  COMPOUNDS.  49 

O.C2Hft 

/O.C.H.        /O.C,H6    \ 

2CS  =  CS  CS 

\S-  \S S/ 

Dimethyl-dithiocarbamic  Acid. — According  to  Schall ' 
the  electrolysis  of  the  potassium  salt  of  dimethyl- 
dithiocarbamic  acid  resulted  in  the  formation  of  tetra- 
ethyl-thiuram  disulphide, 

[CS.N(C,H.),],S,. 

Thiophene. — This  compound  under  the  influence  of 
the  electric  discharge  absorbs  as  much  as  8.6$  of  its 
own  weight  of  nitrogen,  (C4H4S)2N  being  formed 
(Berthelot3). 

1  Ztschr.  f.  Elektroch.,  3,  83. 
*  Ann.  chim.  phys.,  n,  35. 


ELECTROLYSIS  AND  ELECTROSYNTHESIS 
OF  AROMATIC  COMPOUNDS. 


THE  data  on  the  results  of  investigation  in  this 
branch  of  the  subject  are  considerably  more  limited 
than  in  the  case  of  the  aliphatic  series.  One  of  the 
reasons  for  this  is  the  difficulty  with  which  the  ben- 
zene nucleus  undergoes  oxidation,  a  condition  which 
permits  of  comparatively  few  reactions.  Nearly  all 
the  reactions  involve  substituted  groups  only.  In 
almost  all  cases  the  benzene  nucleus  remains  un- 
altered. 

In  accordance  with  the  method  of  presentation  pre- 
viously adopted,  the  investigations  on  the  electrolysis 
of  the  hydroxyl  compounds  will  be  first  discussed  in 
the  following  synopsis. 

i.  Phenols. 

Phenol. — Bunge,1  Bartoli  and  Papasogli 9  submitted 
phenol  to  the  action  of  the  electric  current,  Bunge 

I  Chem.  Ber.,  3,  296. 

II  Gazz.  Chim.,  14,  19. 

51 


52       ELECTROLYSIS  AND   ELECTROS YNTHESIS 

observed  that  the  decomposition  of  potassium  pheno- 
late  was  analogous  to  that  of  an  acid  or  a  salt; 
the  potassium  phenolate  was  split  up  into  K  — 
(cathion)  and  C6H5O — (anion),  the  latter  combining 
with  water  to  form  phenol,  with  the  liberation  of 
oxygen.  Bartoli  and  Papasogli,  on  electrolyzing  solu- 
tions of  phenol  in  potassium  and  sodium  hydroxide, 
and  using  electrodes  of  coke,  graphite,  and  platinum, 
obtained  an  acid  having  the  composition  C7H6O4, 
which  melted  at  93°,  reduced  ammoniacal  silver  solu- 
tion and  Fehling's  solution  on  being  heated,  and  when 
in  aqueous  solution  was  not  precipitated  by  acids. 
When,  however,  coke  was  used  as  the  positive  elec- 
trode, an  extensive  decomposition  of  the  phenol 
occurred  and  a  resin  was  formed. 

On  subjecting  a  neutral  potassium  phenolate  solu- 
tion to  the  action  of  the  electric  current  they  were 
able  to  isolate  a  compound,  C66H48Oa2,  soluble  in  alkali 
and  precipitated  from  such  solutions  by  mineral  acids. 
This  latter  compound  on  being  oxidized  with  nitric 
acid  formed  picric  acid.  When  allowed  to  remain  in 
solution  in  the  presence  of  dilute  acids  for  a  prolonged 
period,  it  underwent  decomposition  according  to  the 
following  equation: 

C,tH<80,,  +  H.O  =  C4,H»0lt  +  C..H..O.. 
The  electrolysis  of  neutral  sodium  phenolate  solu- 


OF  AROMATIC  COMPOUNDS.  53 

tion   gave  an  acid  with   the   formula  CMH,0O8  which 
likewise  is  decomposed  on  boiling  with  dilute  acids: 

C29H3008  =  C17H1006  +  ClaH100,. 

The  compound  C1QH10O8  is  soluble  in  alcohol,  melts 
at  75°,  and  is  isomeric  with  the  hydroquinone  ether, 
obtained  by  Etard  from  chlorchromic  acid  and  phenol. 
It  has  the  composition 


Christomanos 1  observed  that  while  sodium  acts 
only  very  slowly  on  dissolved  monobrom-benzene, 
diphenyl  can  speedily  be  obtained  by  placing  sodium 
in  the  solution  and  connecting  this  metal  with  the 
positive  pole  of  a  battery  of  two  Bunsen  elements, 
whose  electrodes  are  immersed  in  the  solution;  di- 
phenyl is  likewise  obtained  by  using  zinc  instead  of 
sodium. 

Phenyl-mercaptan. — Bunge a  investigated  phenyl- 
mercaptan  in  the  same  manner  as  the  corresponding 
alkyl  compound.  Phenyl-disulphide,  (C.HB)aSa,  was 
formed  at  the  positive  pole. 

1  Gazz.  Chim.,  1875,  p.  402. 
1  Chem.  Ber.,  3,  911. 


54       ELECTROLYSIS  AND   ELECTROSYNTHESIS 


2.  Aldehydes  and  Ketones. 

Benzaldehyde.  —  Kauffmann,1  by  the  electrolysis  of 
benzaldehyde  in  a  12-15$  solution  of  potassium  bi- 
sulphide, obtained  at  the  cathode  a  mixture  of  hy- 
dro-benzoin and  iso-hydrobenzoin.  According  to  his 
statements,2  an  alcoholic  solution  of  sodium  hydroxide 
is  more  suitable  for  the  reaction  than  the  aqueous 
solution  of  bisulphide.  Other  aldehydes  and  ketones 
show  a  behavior  similar  to  benzaldehyde. 

Tetramethyl-diamido-benzophenone.  —  Michler's  ke- 
tone, 

/C6H4N  :  (CH3)9 
J\C6H4N  :  (CH,y 

gives  the  corresponding  benzhydrol, 

/C6H4.N  :  (CH.). 
(HO)CH 

\C.H4.N  :(CH,)a 

Aceto  -  phenone,  C6H6.CO.CHS.  —  Aceto  -  phenone 
yields  aceto-phenone  pinacone, 


C.H  ^-C 

\C(OH).C(OH). 


Ztschr.  f.  Elektroch.,  2,  365. 
4,  461. 


OF  AROMATIC  COMPOUNDS.  55 

Benzile.  —  The  aromatic  di-ketone  benzile,  C,H6CO. 
CO.C6H5,  gives  peculiar  results.  On  reduction  in  an 
alkaline  alcoholic  solution  a  whole  series  of  bodies  is 
formed,  i.e.,  benzoic  acid,  benzilic  acid,  tetraphenyl- 
erythrite,  Ca8H,6O4  = 

C.H^HOH 
CeH5.COH 
C6H,COH 
C.H..CHOH, 

and  a  substance,  C,8Ha6Os,  containing  one  less  atom 
of  oxygen,  which  has  probably  the  constitution 


C.H§.(j;OH 

C,H6.CH 

C8H5.CHOH. 

Tetraphenyl-erythrite  is  also  formed  by  the  direct 
reduction  of  benzoin. 
Anthraquinone, 


H  //CO\C  H 
«    4^6    *' 


According  to  Weizmann,1  this  compound  when  in 
sulphuric  acid  solution  is  converted  by  electrolytic 
oxidation  into  monoxy-,  dioxy-,  and  trioxy-anthra- 

1  French  Pat.  265292. 


56       ELECTROLYSIS  AND   ELECTROS  YN  THE  SIS 

quinone.  The  cathode  fluids  employed  were  solutions 
of  alkalies,  alkali  carbonates,  chromates,  permanga- 
nates, acidulated  water,  and  dilute  acids.  Both  direct 
and  alternating  currents  were  used.  On  the  elec- 
trolysis of  anthraquinone  and  potassium  hydroxide 
alizarine  is  formed. 

Nitro-aldehydes  and  nitro-ketones  will  be  discussed 
in  the  chapter  on  nitro-compounds. 

3.  Acids. 

Benzoic  Acid. — Benzoic  acid  and  its  salts  were  ex- 
amined by  several  investigators,  first  by  Matteuci,1 
then  by  Brester,8  and  most  thoroughly  by  Bourgoin.8 

The  result  of  all  these  investigations  is  to  show 
that  here  no  secondary  reactions  take  place,  as  was 
observed  in  the  case  of  the  fatty  acids,  but  that  the 
only  effect  of  the  current  is  to  produce  a  separation 
into  hydrogen  (or  metal)  and  the  acid  radical,  the 
latter  regenerating  the  acid  at  the  positive  pole.  In 
an  alkaline  solution  it  is  possible  to  so  increase  the 
oxidation  that  the  benzoic  acid  is  destroyed.  The 
decomposition  products  which  then  appear  at  the 
anode  are  carbon  dioxide,  carbon  monoxide,  and 
sometimes  acetylene.  The  odor  of  bitter  almonds  is 
also  frequently  observed.  A  thorough  investigation 

1  Bull.  soc.  chim.,  10,  209. 

»  Jahresb.  f.  Chem.,  1866,  p.  87. 

8  Bull.  soc.  chim.,  10,  431. 


OF  AROMATIC  COMPOUNDS.  57 

on  the  electrolytic  decomposition  of  sodium  benzoate 
was  made  by  Lob.1  He  employed  a  current  having  a 
potential  of  6-7  volts  and  a  current  density  of  15-20 
amp.,  and  obtained  a  small  quantity  of  a  substance 
containing  sodium,  the  empirical  formula  for  which 
was 

C,H.O.Na, 

but  the  chemical  nature  of  which  has  not  yet  been 
determined.  There  is  formed  besides  this  compound 
a  small  amount  of  benzaldehyde,  as  well  as  acetylene 
and  carbon  monoxide.  Under  no  circumstances  do 
diphenyl  or  other  hydrocarbons  occur,  nor  do  fatty 
acids  appear,  which  is  otherwise  generally  the  case  in 
an  oxidation  of  this  character. 

Thio-benzoic  Acid. — On  electrolyzing  this  acid  Bunge' 
obtained  the  bisulphide  of  benzoyl. 

Sulpho-benzoic  Acid. — This  acid  is  not  changed  by 
the  current  according  to  the  statements  of  the  same 
investigator. 

Phthalic  Acid. — Bourgoin  *  states  that  the  electrolysis 
of  this  acid  and  of  its  neutral  or  alkaline  salts  resulted 
in  the  formation  of  the  unchanged  acid  at  the  positive 
pole.  The  appearance  of  small  quantities  of  carbon 
dioxide  and  carbon  monoxide,  however,  was  an  evi- 


1  Zeitschr.  f.  Elektroch.,  2,  663,  ibid.,  3,  3. 

J  Chem.  Ber.,  3,  296. 

8  Jahresb.  f.  Chem,,  1871,  p.  631. 


58       ELECTROLYSIS  AND   ELECTROS YN THESIS 

dence  that  a  small  portion  of  the  acid  had  undergone 
oxidation. 

The  potassium  salt  of  the  mono-ethyl  ester  of 
phthalic  acid,  when  electrolyzed  by  Brown  and 
Walker,1  became  dark-colored  and  a  resinous  sub- 
stance was  formed,  but  the  isolation  of  any  new 
electrolytic  product  was  not  possible. 

Phenyl-acetic  Acid. — This  acid  electrolyzed  in  the 
form  of  its  potassium  salt  by  Slawik8  yielded  free 
phenyl-acetic  acid. 

Cinnamic  Acid. — Cinnamic  acid,  investigated  by 
Brester,8  showed  a  similar  behavior  in  the  electrolysis 
of  both  the  free  acid  and  the  neutral  solutions  of  its 
salts. 

Benzyl-malonic  Acid. — When  this  acid  in  the  form 
of  its  ethyl-potassium  salt  was  submitted  to  elec- 
trolysis by  Brown  and  Walker4  it  showed  a  behavior 
materially  different  from  that  of  malonic  acid.  The 
solution  became  dark-colored  and  contained  no  new 
compound.  If  oxidation  occurred  it  was  a  complete 
oxidation  into  carbon  dioxide  and  carbon  monoxide, 
such  as  has  been  observed  in  the  case  of  the  unsatu- 
rated  acids. 


1  Lieb.  Ann.,  274,  67. 

9  Chem.  Ber.,  7,  1051. 

•  Jahresb.  f.  Chem.,  1866,  p.  87. 

4  Lieb.  Ann.,  274,  67. 


OF  AHOMAT1C  COMPOUNDS. 


4.  Amido-Compounds. 

Aniline. — Destrem  *  investigated  the  action  of  the 
electric  spark  from  an  induction  apparatus  on  aniline 
vapor  and  observed  a  decomposition  into  acetylene, 
hydrogen,  hydrocyanic  acid,  and  nitrogen.  E.  Ro- 
tundia  electrolyzed  aniline.  Since  pure  aniline  is  an 
extremely  poor  conductor  he  made  the  solution  suit- 
able for  electrolysis  by  the  addition  of  ammonia. 
After  a  period  of  three  days,  during  which  hydrogen 
was  continually  evolved  at  the  negative  pole  and  a 
tarry  substance  was  deposited  at  the  positive  pole, 
Rotundi  interrupted  the  electrolysis  and  was  able,  with 
more  or  less  certainty,  to  establish  the  following 
processes : 

1.  The  formation  of  diazo-compounds: 

CeH6NHa(HNO.)  +  HNOa  =  C6H6N3NO,  +  2HSO. 

2.  The  formation  of  diazo-amido-compounds: 

2CflHBNHa  +  HNO,  =  C6H6N3NHC6H6  +  2H3O. 
C9H5N2NO3  +  C6H6NHa  =  CeH6NaNH.C8H6  +  HNO,. 

3.  The  formation  of  azo-compounds  by  direct  oxi- 
dation of  aniline: 

2C6H6NH,  +  2O  =  2H3O  +  C6H6NaC6H6. 

1  Jahresb.  f.  Chem.,  1884,  p.  272. 

2  Atti.  d.   R.  Acad.  d.  Scienze  d.    Torino,  39,  4  ;   Jahresb.  f. 
Chem.,  1884,  p.  270. 


6O       ELECTROLYSIS  AND   ELECTROSYNTHESIS 

4.  The  formation  of  amido-azo-compounds  by 
molecular  rearrangement  of  diazo-amido-compounds. 
The  nitrous  and  nitric  acids  were  oxidation  products 
of  the  ammonia  which  was  added. 

INVESTIGATIONS  OF  GOPPELSROEDER.' 

These  relate  to  aniline  and  its  derivatives,  and  aim 
at  preparing  the  most  important  dyes  of  the  aniline 
series.  Although  the  reactions  which  take  place  in 
the  cell  have  not  as  yet  been  explained,  the  researches 
form  valuable  material  for  consideration.  Goppels- 
roeder  has  gathered  the  technical  results  in  a  small 
pamphlet:  "  Farbelektrochemische  Mitteilungen " 
(Muhlhausen,  1889). 

If  a  galvanic  current  is  conducted  through  acid  or 
neutral  aqueous  solutions  of  aniline  there  is  formed  at 
the  positive  pole,  besides  other  coloring  matters,  ani- 
line black,  C24HaiN4Cl.  Under  similar  conditions  dyes 
are  obtained  at  the  positive  pole  from  the  salts  of 
toluidene,  methyl- aniline,  diphenylamine,  ditolylamine 
and  phenyl-tolylamine. 

Naphthylamine  salts  give  naphthylamine  violet.  On 
electrolysis  of  anthraquinone  and  potassium  hydroxide, 
Goppelsroeder  succeeded  in  obtaining  alizarine.8 

1  Dingier,  Polytech.  Journal,  221,  75;  ibid.,  223,  317  and  634; 
ibid.)  224,  92  and  209. 
*  See  also  p.  56. 


OF  AROMATIC  COMPOUNDS.  6 1 

All  these  reactions  are  to  be  attributed  to  the  action 
of  electrolytic  oxygen.  In  the  brief  survey  which 
will  here  be  given  it  is  not  possible  to  go  into  the 
details  of  the  researches.  The  following  literary  data 
will  serve  as  a  guide: 

Research  I.1  Preparation  of  aniline  black. 

Research  2.2  Electrolysis  of  aniline  with  excess  of 
aniline.  Electrolysis  of  toluidene.  Electrolysis  of 
mixtures  of  aniline  with  toluic  acids. 

Research  3.'  Electrolysis  of  aniline  and  toluidene 
salts  in  the  presence  of  nitrate,  nitrite,  or  chlorate  of 
potassium  in  aqueous  solution. 

Research  4."  Electrolysis  of  the  salts  of  methyl- 
aniline.  Electrolysis  of  the  salts  of  diphenylamine. 
Electrolysis  of  the  salts  of  methyl-diphenylamine. 
Electrolysis  of  phenol.  Electrolysis  of  the  salts  of 
naphthylamine. 

Research  5.5  Conversion  of  anthraquinone  into  ali- 
zarine by  the  electrolysis  of  a  mixture  of  anthra- 
quinone and  potassium  hydroxide. 

Liebmann's fl  attempts  to  make  quinone  by  the 
electrolytic  oxidation  of  aniline  or  electrolytically 
prepared  aniline  black  were  unsuccessful. 

1  Dingier,  Polytechn.  Journ.,  221,  75. 
*  Ibid.,  223,  317. 

3  Ibid.,  223,  634. 

4  Ibid.,  224,  92. 

6  Ibid.,  224,  209. 

'  Ztschr.  f.  Elektroch.,  2,  497. 


62       ELECTROLYSIS  AND   ELECTROS 'YN THESIS 

Hydroquinone  in  an  aqueous  solution  acidified  with 
sulphuric  acid  could  be  quantitatively  converted  into 
quinone  at  the  anode: 

2C.H4(OH)a  +  O  =  H,0  +  C6H4(OH)a.C,H40, 

The  same  compound  was  also  formed  when  alter- 
nating currents  were  used. 

Voigt,1  by  the  electrolytic  oxidation  of  suitable 
mixtures  of  bases,  prepared  rosaniline,  chrysaniline, 
safranine,  and  p-leucaniline.  His  object  in  these 
researches  was  the  same  as  that  of  Goppelsroeder; 
namely,  the  preparation  of  the  important  dyes  of  the 
aniline  series. 

If  electrolytic  oxygen  is  permitted  to  act  upon 
aniline,  dissolved  in  concentrated  acetic  acid  solution, 
acetanilide  is  formed;  by  using  a  dilute  solution, 
however,  amido-hydroquinone  is  obtained. 

So  far  as  can  be  learned  from  the  literature  these 
investigations  have  not  been  concluded,  which  is  also 
the  case  with  those  of  Poising,8  who  by  the  oxidation 
of  p-phenylene-diamine  obtained  a  beautiful  blue  dye 
similar  to  indigo. 

Poising  obtained  p-phenylene-diamine  by  the  elec- 
trolytic reduction  of  amido-azo-benzene. 

From  the  electrolysis  of  benzene -p-phenylene-diamine 


1  Ztschr.  f.  angew.  Chem.,  1894,  p.  107. 
1  Ztschr.  f.  Elektrochemie,  2,  30. 


OF  AROMATIC  COMPOUNDS.  63 

there  likewise  resulted  at  the  anode  a  blue  dye,  which 
showed  a  behavior  analogous  to  that  of  the  dye 
obtained  from  p-phenylene-diamine. 

5.  Electrolytic  Reduction  of  Nitro-Compounds. 

In  general,  azo-,  hydrazo-,  and  amido-compounds 
result  from  the  electrolytic  reduction  of  nitro-com- 
pounds.  In  this  way  Kendall 1  obtained  aniline  from 
nitre-benzene,  and  Elbs a  and  Haussermann  *  prepared 
the  normal  reduction  products  of  nitfo-phenol.  The 
formation  of  azoxy-,  azo-,  amido-,  or  hydrazo-com- 
pounds  was  dependent  upon  whether  acid  or  alkaline 
solutions  were  employed.  If  nitro-benzene  is  reduced 
in  a  concentrated  acetic  or  formic  acid  solution,  to 
which  a  few  drops  of  concentrated  sulphuric  acid 
(to  increase  the  conductivity)  have  been  added,  the 
corresponding  salts  of  benzidene  result;  a  fact  further 
confirmed  by  Lob.4 

According  to  the  investigations  of  the  same  author, 
in  the  electrolysis  of  an  ammoniacal  solution  azo- 
benzene  is  formed  as  the  chief  product  and  hydrazo- 
benzene  as  a  secondary  product. 

Gattermann  and  Koppert  *  obtained  p-amido-phenol- 


1  German  Pat.,  21131. 

2  Journ.  prakt.  Chem.,  49,  39. 
1  Chem.  Zeitung,  17,  129,  209. 

4  Ztschr.  f.  Elektrochem.,  3,  471. 

5  Chem.  Zeitung,  17,  210. 


64       ELECTROLYSIS  AND   ELECTROS 'YN THESIS 

sulphate  by  the    reduction   of  nitro-benzene-sulphonic 
acid. 

Noyes  and  Clement,1  on  the  reduction  of  nitro- 
benzene in  a  concentrated  sulphuric  acid  solution, 
obtained  p-amido-phenol-sulphonic  acid.  Gatter- 
mann,a  starting  with  a  similar  solution,  by  varying 
the  conditions  of  the  experiment  obtained  directly 
p-amido-phenol.  He  explains  the  reaction  by  assum- 
ing the  intermediate  formation  of  phenyl-hydroxyl- 
amine,  which  on  further  reduction  changes  by  molec- 
ular rearrangement  into  the  final  product.  By  similar 
treatment  were  formed: 

an    amido-cresol-monosulphonic    acid3  from     o-nitro- 

toluene; 

the  o-p-diamido-phenol  from  m-dinitro-benzene; 
diamido-cresol  from  o-p-dinitro-toluene; 
o-p-diamido-phenol  from  m-nitr  aniline; 
a  diamido-cresol  from  o-nitro-p-toluidene; 
the  same  diamido-cresol  from  p-nitro-o-toluidene; 
an  amido-salicylic  acid  from  m-nitro-benzoic  acid; 
an  amido-cresotinic  acid  from  m-nitr  o-p-toluic  acid; 
a  corresponding  amido-oxy  acid  from  nitro-terephthalic 

acid; 
a  corresponding  amido-oxy-acid  from  nitro-isophthalic 

acid; 

1  Chem.  Ber.,  26,  990. 
8  Ibid.,  26,  1840. 
8  Ibid.,  27,  1929. 


OF  AROMATIC  COMPOUNDS.  65 

an  amido-naphthalene-sulphonic  acid  from  a^oe^-nitro- 
naphthalene-sulphonic  acid. 

The  following  is  true  in  all  these  cases  where  the 
reduction  is  carried  out  in  a  concentrated  sulphuric 
acid  solution: 

The  nitro-groups  are  completely  reduced  to  amido- 
groups  and  a  hydroxyl-group  is  taken  up,  always  in  a 
para-position  to  one  of  the  amido-groups.  As  in  the 
case  of  o-nitro-toluene  sometimes  also  a  sulpho-group 
is  taken  up.  p-nitro-  toluene  on  electrolysis  behaves 
differently.  Here  the  final  product  has  the  composi- 
tion C14HuN,Oa,  and  its  formation  is  as  follows: 

p-Amido-benzyl  alcohol  is  formed  from  p-tolyl- 
hydroxylamine  (an  intermediate  product  in  the  reduc- 
tion of  p-nitro-toluene)  by  molecular  rearrangement, 

_          /CH3OH 


The  amido-benzyl  alcohol  thus  formed  condenses 
with  one  molecule  of  nitro-toluene  (under  the  influ- 
ence of  the  sulphuric  acid),  water  being  split  off  '  : 

u  /CH,OH   ,   r  TT  /CH,  _ 
'H«  Cehl*\N03 

nitro-amino-o-benzyl-toluene, 
C.H4-  -CH  -C6H8/™3  +  Ha0 


1  Chem.  Ber.,  26,  2810, 


66       ELECTROLYSIS  AND   ELECTROS  YN  THE  SIS 

In  a  third  paper1  Gattermann  applies  this  reduction 
to  a  large  number  of  compounds  which  for  lack  of 
space  cannot  here  be  enumerated.  The  nature  of  the 
reaction  is  the  same  in  all  cases.  The  esters  of  the 
carboxylic  acids  show  the  same  behavior  as  the  acids 
themselves. 

These  reduction  products  have  all  become  the  sub- 
jects of  patents.2 

Lob  and  Gattermann  have  produced  direct  and  in- 
direct evidence  that  the  amido-phenols  are  actually 
formed  by  the  molecular  rearrangement  of  phenyl- 
hydroxylamine,  which  occurs  as  an  intermediate 
product. 

Lob3  has  found  that  p-  and  o-chlor-aniline  are  ob- 
tained by  the  electrolytic  reduction  of  nitro-benzene 
suspended  in  fuming  hydrochloric  acid,  nitro-benzene 
dissolved  in  alcoholic  hydrochloric  acid,  and  nitro- 
benzene dissolved  in  mixtures  of  hydrochloric  and 
acetic  acid.  With  hydrobromic  acid  the  correspond- 
ing brom-anilines  are  formed. 

The  reaction  takes  place  as  shown  in  the  following 
equations: 


2.  C6H6NHOH+  HCl  =  C6H6NHCl+HaO 


1  Chem.  Ber.,  2J,  1927. 

*  German  Patent,  75260  and  additions  to  the  same, 

3  Ztschr.  f.  Elektrochem.,  3,  46. 


OF  AROMATIC  COMPOUNDS.  67 

3.  C,H6NHC1  = 

NH, 

^CC1     and     HC 

I  II  I  UNIVERSIT 


NH. 


H 


Cl 


The  phenyl-chloramine  formed  by  the  action  of 
hydrochloric  acid  on  phenyl-hydroxylamine  changes, 
by  molecular  rearrangement,  into  o-  and  p-chlor- 
aniline. 

Gattermann1  has  obtained  direct  proof  of  the  inter- 
mediate formation  of  phenyl-hydroxylamine  by  adding 
benzaldehyde  to  the  solution  at  the  beginning  of  the 
electrolysis.  He  was  thus  able  to  isolate  a  condensa- 
tion product  of  phenyl-hydroxylamine  with  benzalde- 
hyde. In  this  way  he  obtained  benzylidene-phenyl- 
hydroxylamine, 

O 

C.H6N-    -CH,C6H6, 

from  nitre-benzene  ',  benzy  lidene-o-tolyl-hydroxylamine, 


C6H6.CH  -  N.C6H6.CH8, 

from  o-nitro-toluene,  and  the  corresponding  benzyl- 
idene  compounds  from  m-nitro-toluene,  p-nitro-toluene, 
nitro-p-xylene,  and  m-nitro-benzoic  acid. 

The  presence   of  formaldehyde  in   the  electrolytic 
1  Chem.  Ber.,  29,  3040. 


68       ELECTROLYSIS  AND    ELECTROS YN THESIS 

reduction  of  nitro-compounds  produces  an  effect 
entirely  different  from  that  caused  by  the  addition  of 
benzaldehyde.  The  phenomena  occurring  in  this  case 
have  been  thoroughly  investigated  by  Lob.1 

The  fundamental  object  of  his  researches  differs 
from  that  of  Gattermann,  in  that  Lob  undertakes  to 
establish  the  separate  phases  of  the  reduction  of  the 
nitro-group. 

This  he  accomplishes  by  the  addition  of  formal- 
dehyde to  the  electrolyte  under  varying  conditions, 
and  as  a  result  the  intermediate  products,  at  the 
moment  of  their  formation,  combine  with  formal- 
dehyde, producing  condensation  compounds  which  do 
not  undergo  further  decomposition.  By  regulating 
the  potential  and  density  of  the  current  the  reaction 
can  at  will  be  checked  at  a  perfectly  definite  phase  of 
the  reduction. 

In  the  electrolysis  of  nitro-benzene  by  this  method 
there  were  formed : 

1.  p-Anhydro-hydroxylamine-benzyl  alcohol, 

,H/NH.OH     „ 
'•n*\CH3OH      n' 

which  may  also  be  directly  prepared  by  the  action  of 
formaldehyde  on  phenyl-hydroxylamine. 

2.  Methylene-di-p-anhydro-amido-benzyl  alcohol, 


F        /NH.C.H.CH^ 
LCH'\NH.C6H4CH2/ 


Ztschr.  f.  Elektroch.,  4,  428. 


OF  AROMATIC  COMPOUNDS.  69 

a  condensation    product  of  formaldehyde  and  aniline. 

The  behavior  of  p-nitro-toluene  is  different,  since  in 
this  case,  the  p-position  being  occupied  by  the  nitro- 
group,  an  analogous  reaction  with  formaldehyde  is 
impossible. 

While  p-nitro-toluene  is  converted  in  an  alkaline 
solution  smoothly  into  azo-toluene  and  in  an  acid 
solution  into  p-toluidene,  nearly  equal  quantities  of 
two  different  products  are  obtained  in  the  presence  of 
formaldehyde,  viz.  : 

1.  p-Dimethyl-toluidene. 

2.  Dimethylene-ditoluidene. 

The  nature  of  the  reaction  is  such  that  the  reduc- 
tion proceeds  until  p-toluidene  is  formed,  and  not  till 
then  does  a  condensation  with  formaldehyde  occur: 
2C6H4.CH8.NHa  +  2CH20  = 


2H,O. 


The  dimethylene-ditoluidene  thus  formed  on  further 
reduction  breaks  up  into  dimethyl-toluidene  and 
toluidene,  the  latter  becoming  again  subject  to  the 
action  of  the  formaldehyde  : 


f  4H=* 

CH8,C6H4.N(CH8)a  +  HsN.C.HiCHi. 
A  state  of  equilibrium  exists  between  the  dimethyl- 


7O       ELECTROLYSIS  AND   ELECTROSYNTHESlS 

toluidene  and  the  dimethylene-ditoluidene  at  the  end 
of  the  operation. 

A  further  application1  of  Gattermann's  reaction 
has  been  found  in  the  case  of  aromatic  nitr amines* 
which  if  reduced  in  a  concentrated  solution  of  sul- 
phuric acid  give  amido-phenol  derivatives.  The 
process  can  also  be  applied  to  the  esters  of  nitro- 
carboxylic  acids 8  and  results  in  the  formation  of 
amido-phenol-carboxylic  esters. 

Nitro-sulphonic  acids  *  show  a  similar  behavior, 
while  the  p-nitro-  or  p-nitroso-alkyl-anilines*  and 
toluidenes,  as  the  case  may  be,  are  reduced  to 
p-amido-derivatives  of  alkylated  m-oxy-anilines  or 
their  homologues. 

The  nitro-derivatives  of  the  quinoline*  series  show  a 
deportment  similar  to  that  of  the  derivatives  of 
benzene. 

Nitre-aldehydes  ^  which  Gattermann  7  has  also  chosen 
for  the  subject  of  thorough  investigation,  conduct 
themselves  differently  from  the  nitro-compounds  thus 
far  described. 

If  the  nitro-aldehydes  are  reduced  there  are  formed 
either  the  free  aldehyde-phenyl-hydroxylamines,  or 

German  Pat.,  77806. 

Ibid..  78829. 

Ibid..  79865. 

Ibid.,  81621. 

Ibid...  81625. 

Ibid.,  80978. 

Chem.  Ber.,  29,  3037;  German  Pat.  85198. 


OF  AROMATIC  COMPOUNDS.  7  1 

condensation  products  of  the  same  with  the  nitro- 
aldehyde  present.  The  nitro-benzylidene-aldehydo- 
phenyl-hydroxylamines  are  thus  formed  : 

+  4H  =  H'°  +  C«H'\NHOH. 


2. 


/CHO 
U«H«\       /O\ 

\N  -  CH.C6H4.NO9. 

p-Nitro-benzylidene-p-aldehydo-phenyl-hydroxylaminey 

C.CHO  C.NO, 

#     \  /     ^ 

HC          CH  HC         CH 

I  II  II  I       ' 

HC         CH  HC         CH 

V/      /o\       \c// 

_N  --  CH- 

may  thus  be  prepared  from  p-nitro-benzaldehyde. 

From  m-nitro-benzaldehyde  an  analogous  compound 
is  formed. 

Gattermann,1  on  reducing  several  aromatic  nitro- 
ketones,  obtained  the  corresponding  derivatives  of 
amido-phenols. 

By  a  similar  treatment  amido-oxy-acetophenone, 


1  Chem.  Ber.  ,  29,  3034. 


72       ELECTROLYSIS  AND   ELECTROS  YNTHESIS 

is  formed  from  m-nitro-acetophenone  ;  amido-oxy-ben 
zophenone, 


from  m-nitro-benzophenone  ;  and  amido-oxy-phenyl-p- 
tolylketone, 


from  m-nitro-phenyl-p-tolylketone. 

The  process  which  Straub  '  employs  to  prepare 
hydrazo-compounds  from  nitro-hydrocarbons  is  yet  to 
be  mentioned.  The  chief  feature  of  his  experiments 
is  that  the  original  material  and  all  intermediate 
products  are  retained  in  solution  during  the  electroly- 
sis by  the  selection  of  a  suitable  solvent,  and  the 
hydrazo-compounds  are  withdrawn  from  the  action  of 
the  current  by  precipitation. 

Straub  attains  this  end  by  subjecting  the  nitro- 
hydrocarbons  to  electrolytic  reduction  in  a  solvent 
made  a  conductor  by  the  addition  of  potassium  hy- 
droxide. The  quantity  of  the  liquid  used  must  be 
sufficient  to  keep  in  solution  the  azo-  and  azoxy-com- 
pounds  corresponding  to  the  nitro-hydrocarbon. 

Noyes  and  Dorrance  3  have  applied  Gattermann's 
reaction  to  p-nitraniline  and  some  other  substances. 
In  this  way  they  obtained  p-diamido-benzene  sulphate 

1  German  Patent,  79731. 
8  Chem.  Ber.,  28,  2349. 


OF  AROMATIC  COMPOUNDS.  73 

from  p-nitr  aniline,  p-ami^o-phenol-sulphonic  acid 
from  p-nitro-phenol,  and  p-amido-phenol-sulphonic 
acid  from  p-chlor-nitro-benzene. 

They  explain  the  reactions  in  the  following  manner: 


C  H  '          C  H 

(-'H'CH,  "      C'H'\CH,OH, 


.  /NO, 
C6HS  —  CH3     — 
\NHa 

/NO, 


The  phenomena  of  the  reduction  of  nitro-com- 
pounds  in  alkaline  solution  have  been  investigated  by 
Lob.1  In  his  first  experiments  he  used  nitro-benzoic 
acids  and  nitro-phenols.  It  was  found  that  m-nitro- 
and  p-nitro-benzoic  acid  were  smoothly  reduced  to  the 
corresponding  azo-acids,  while  the  o-acid  under  simi- 
lar conditions  yielded  o-azoxy-benzoic  acid  and  o-hy- 
drazo-benzoic  acid.  The  nitro-phenols  in  alkaline 
solutions  gave  amido-phenols. 

The  fact  that  the  reduction  in  an  alkaline  solution 
may  be  carried  as  far  as  the  azo-phase  has  been  made 

1  Zeitschr.  f.  Elektroch.,  2,  529:  ibid.,  3,  45. 


74       ELECTROLYSIS  AND   ELECTROS  YN  THESIS 

use  of  by  Lob  *  in  performing  a  direct  electrosynthesis 
of  the  mixed  azo-bodies  and  azo-dyes.  The  com- 
ponents of  the  compounds  desired,  in  exactly  equi- 
molecular  proportions,  are  reduced  under  conditions 
which  render  the  union  of  the  two  residues  possible. 
In  this  way  azo-compounds  are  obtained  in  which  the 
substituents  are  in  the  meta-position — compounds 
which  could  not  be  prepared  by  the  Griess  method. 

Kaufmann  and  Hofa  subjected  m-nitro-benzal- 
dehyde  to  reduction  in  alkaline  solution  and  thus 
obtained  m-azo-benzoic  acid  as  the  principal  product 
and  m-azo-benzyl  alcohol  as  a  secondary  product.  By 
the  electrolysis  of  m-nitro-benzaldehyde  Lob 3  ob- 
tained m-azo-benzoic  acid  and  m-azo-benzyl  alcohol 
as  secondary  products.  The  chief  product  consisted 
of  a  mixed  azo-body,  azo-m-benzyl-alcohol-m-benzoic 
acid, 

m  -  CH3OH.C6H4.N :  N.C,H4.COOH  -  m. 

The  Gesellschaft  f.  Chem.  Industrie  of  Basel* 
prepare  orange  dyes  by  using  as  cathode  fluid  an 
alkaline  solution  of  the  yellow  condensation  products 
of  p-nitro-toluene-sulphonic  acid, 

CH'-C«H'\S03H 

1  Ztschr.  f.  Elektroch.,  4,  530. 
8  Chemiker  Zeitung,  1896. 
*  Ztschr.  f.  Elektroch.,  4. 
4  English  Pat.,  22482. 


OF  AROMATIC  COMPOUNDS.  ?5 

(namely,  a  mixture  of  azoxy-stilbene-disulphonic  acid, 
azo-stilbene-disulphonic  acid,  and  dinitro-stilbene- 
disulphonic  acid). 

The  reduction,  however,  must  not  be  continued 
until  amido-compounds  result.  Other  reduction 
processes  are  used  by  the  Badische  Aniline  u. 
Sodafabrik  '  for  making  naphthazarine  from  a^a- 
dinitro-naphthalene  or  a^a^-dinitro-naphthalene.  In 
these  cases  intermediate  products  are  first  formed  in 
the  electrolytic  reduction,  and  these  are  transformed 
into  naphthazarine  by  heating. 

The  Basel  company2  mentioned  above  obtains 
triphenyl-methane  dyes  by  the  electrolytic  reduction 

of    nitro-leuco-bodies   of    the   type  NOa  —  CeH4.CHRa, 

(4)  (i) 

which  result  in  the  formation  ofthecarbinoles 
NH-C,H4.COH.R,° 

(4) 


Ahrens4  accomplished  the  electrolyut  reduction  of 
py.ridine  and  the  derivatives  of  pyridine,  and  obtained 
piperidine  from  pyridine,  and  pipecoline  from  pico- 
line.  In  these  electrolyses  lead  cathodes  and  10$ 
solutions  of  sulphuric  acid  were  employed. 

If  strong  sulphuric   acid  and   a  platinum   cathode 

1  German  Pat.,  79406. 
*  German  Pat.,  84607. 

3  In  these  formulae  A"  denotes  aromatic  radicals  with   primary, 
secondary,  or  tertiary  amido-groups,  or  with  hydroxyl-groups. 

4  Ztschr.  f.    Elektroch.,  2,  577,  580. 


?         ELECTROLYSIS  AND   ELECTROSYNTHESIS 

were  used  there  was  formed  a  substance  containing 
nitrogen  and  sulphur,  the  chemical  nature  of  which 
has  not  yet  been  determined. 

Nitro-piperidines  on  electrolytical  reduction  give 
piperylhydrazines,  ammonia  is  split  off,  and  piper- 
idine  is  in  part  regenerated. 

Nitroso-a-pipecoline  gives,  in  addition  to  ammonia, 
<*-pipecoline  and  a-methyl-piperylhydrazine. 

In  a  like  manner  from  nitroso-aldehyde-copellidine 
(CH3.C2HB.C6H8:  N.NO)  there  is  formed  ammonia,  a 
large  proportion  of  copellidine  (CH3.CaHB.C5H8:  NH), 
and  also  the  corresponding  methyl-ethyl-piperylhy- 
drazine: 

CH3.CaH5.C6H8:N.NHa. 

Quinoline  in  10$  sulphuric-acid  solution  gave  a 
polymeric  dihydro-quinoline  and  tetrahydro-quinoline 
(Ahrens '). 

Quinaldine,  likewise  in  sulphuric-acid  solution,  gave 
dihydroquinaldine  and  tetrahydro-quinaldine. 

6.  Electrolytic  Oxidation  of  Nitro-compounds. 

The  influence  which  the  nitroso-  and  nitro-groups 
exert  on  the  other  substituents  is  especially  shown  in 
oxidation  reactions,  which  here  occur  much  more 
readily  than  in  the  case  of  compounds  which  have  not 

1  Chem.  Ber.,  29,  1123. 


OF  AROMATIC  COMPOUNDS.  TJ 

been  nitrated.  By  the  electrolytic  oxidation  of  nitroso- 
piperidine  Ahrens '  obtained  dipiperidyl  (C10HaoNQ). 
Elbs3  secured  a  satisfactory  yield  of  p-nitro-benzyl 
alcohol  from  p-nitro -toluene. 

The  introduction  of  hydroxyl-groups  into  azo-ben- 
zene,  which  Heilpern 3  succeeded  in  accomplishing, 
can  also  be  regarded  as  an  oxidation  process.  If  azo- 
benzene  be  dissolved  in  as  small  a  quantity  of  cone, 
sulphuric  acid  as  possible  and  this  solution  be  sub- 
jected to  electrolytic  action  at  the  anode,  chiefly  tetra- 
oxy-azo-benzene  is  formed : 

C13H10O4Na  =  (OH)2C6H,N  :  NC6H8(OH)a. 

According  to  a  patent 4  benzoyl-sulphone-imides  can 
be  prepared  by  the  electrolytic  oxidation  of  toluene- 
sulphone -amides ;  for  example,  o-benzoyl-sulphone- 
imide,  or  saccharine,  from  o-toluene-sulphone-amide : 


"""•XCH,        '+3°       C61 

The    corresponding    p-compound,    and    p-nitro-o- 
toluene-sulphone-amide,  . 

NO9.CH3.C9H,.SO,NH, 
show  a  similar  behavior. 

Yellow  mordant  dyes  are  obtained  by  the  Badische 
Aniline  u.  Sodafabrik  *  by  the  oxidation  of  aromatic 

1  Ztschr.  f.  Elektroch.,  2,  579. 

*  Ibid.t  2,  522. 

•  Ibid.,  4,  89. 

4  F.  v.  Heyden's  Nachfolger,  German  Pat..  85491. 
6  German  Pat.,  85390. 


78       ELECTROLYSIS  AND   ELECTROS YN THESIS 

oxycarboxylic  acids  in  sulphuric  acid  solution,  by  the 
use  of  ammonium  persulphate  or  by  electrolysis.  A 
whole  series  of  acids  have  been  investigated:  m-dioxy- 
benzoic  acid,  gallic  acid,  tannin,  the  ethyl  ester  of  gallic 
acid,  gallamide  ((OH)sC8HaCO.NH2),  o-,  m-,  and 
p-oxy-benzoic  acids,  cresotinic  acid,  etc. 

7.  Electrolysis  of  Alkaloids.1 

Caffeine,  Theine,  C8H]0N4O2. — On  permitting  the 
electric  current  to  act  for  several  days  on  a  solution 
of  caffeine  acidified  with  sulphuric  acid  Pommerehne  * 
obtained  amalic  acid,  formic  acid,  ammonia,  and 
methylamine. 

Atropine,  C1TH23NO3. — From  the  neutral  sulphate  of 
atropine  crystallized  atropine  is  gradually  precipitated 
at  the  cathode,  while  at  the  anode  carbon  dioxide, 
carbon  monoxide,  oxygen,  and  nitrogen  are  evolved. 
The  acid  sulphate  behaves  in  a  similar  manner,  but 
the  evolution  of  nitrogen  was  not  observed. 

Opium. — If  opium  is  subjected  to  the  action  of  the 
electric  current  the  acid  goes  to  the  cathode  and  the 
base  to  the  anode.  Thus  meconic  acid  (oxy-pyrone- 
dicarboxylic  acid)  was  found  at  the  positive  pole  and 
morphine  (C17H17NO(OH)2)  at  the  negative  pole. 


1  Donate  Tommasi:  Trait6  d'Electrochimie,  Th6orique  et  Prac- 
tique,  Part  4,  788. 

2  Arch.  f.  Pharm.,  235,  364. 


OF  AROMATIC   COMPOUNDS.  79 

Bourgoin,  however,  showed  that  the  reaction  does 
not  take  place  smoothly,  but  is  always  accompanied 
by  secondary  reactions. 

Morphine. — Pommerehne,1  by  the  electrolysis  of  a 
solution  of  morphine  acidified  with  sulphuric  acid, 
obtained,  after  a  few  days,  crystals  of  oxy-dimorphine 
sulphate.  The  solution  became  dark-colored. 

Codeine  (methyl-morphine), C17H17NO(OH)O.CH,.— 
On  the  electrolysis  of  the  neutral  sulphate  hydrogen 
is  evolved,  codeine  is  precipitated,  and  the  solution 
turns  brown.  The  acid  sulphate  undergoes  more 
complete  decomposition,  and  carbon  dioxide,  carbon 
monoxide,  oxygen,  and  nitrogen  are  split  off. 

Cotarnine,2  CiaH1BNO4. — This  compound  is  converted 
by  the  electrolytic  hydrogen  quantitatively  into  pure 
hydro-cotarnine, 

(C,,H,tNO,),.H,0. 

Quinine,  CaoHa4NaO2. — Although  the  neutral  sul- 
phate is  a  very  poor  conductor,  the  acid  sulphate  is 
readily  decomposed  into  carbon  dioxide,  carbon  mon- 
oxide, and  nitrogen.  The  color  of  the  solution 
changes  to  a  dark  brown. 

Cinchonine,3  C19H2QN2O. — On  the  electrolysis  of  the 
nitrate  of  this  compound  an  oil-like  body  appears  at 
the  anode. 

1  Arch.  f.  Pharm.,  235,  3*4. 

*  German  Pat.,  94949. 

3  Journ.  prakt.  Chem.,  72,  73. 


80       ELECTROLYSIS  AND    ELECTROS YNTHESIS 

Strychnine,1  C31HaaNaOa. — The  neutral  sulphate 
suffers  but  little  change.  The  solution  becomes 
slightly  colored,  hydrogen  and  oxygen  are  given  off, 
and  crystals  of  strychnine  collect  on  the  cathode. 

The  acid  sulphate  behaves  in  a  like  manner,  except 
that  in  its  case  the  formation  of  carbon  dioxide  and 
carbon  monoxide  as  well  as  oxygen  and  nitrogen 
shows  that  a  part  of  the  substance  undergoes  complete 
decomposition.  In  strongly  acid  solutions  the  split- 
ting off  of  nitrogen  does  not  occur. 

Brucine,1  C83H26NaO4. — A  solution  of  the  neutral 
sulphate  turns  red  and  the  sulphate  is  decomposed. 
Hydrogen  is  evolved  at  the  negative  pole,  but  the 
brucine  completely  absorbs  the  oxygen  at  the  positive 
pole.  The  acid  salt  is  very  energetically  decomposed, 
becoming  first  red  and  then  brown.  At  the  anode 
carbonic-acid  gas,  carbon  monoxide,  oxygen,  and  ni- 
trogen escape. 

Besides  the  gases  mentioned,  the  above  alkaloids 
break  up  into  other  products,  principally  complicated 
compounds  containing  nitrogen. 

8.  Camphor  and  Glucosides. 

Terpentine  hydrochloride. — This  compound  on  elec- 
trolysis in  the  melted  condition  or  in  an  alcoholic 
acetic-acid  solution  gave  camphor,  C10H16O  (Richard- 
son a). 

1  Bull.  soc.  chim.,  12,  400. 
J  English  patent,  3555. 


OF  AROMATIC  COMPOUNDS.  8 1 

Salicine,  C1SH18OV — Salicine  on  electrolysis  yielded 
salicylic  aldehyde  and  salicylic  acid  (Tichanowitsch1). 

9.  Electrolysis  of  Blood. 

The  defibrinated  blood  of  a  dog  was  submitted  to 
electrolysis  by  Becquerel.  He  made  use  of  platinum 
electrodes  and  a  current  furnished  by  a  battery  of 
three  Daniel  cells.  At  the  negative  pole  he  observed 
the  following  phenomena: 

The  blood  became  brown  and  alkaline,  and  con- 
tained neither  white  nor  red  corpuscles;  it  possessed 
the  property  of  gradually  dissolving  blood-corpuscles 
and  had  the  odor  of  putrid  meat. 

At  the  positive  pole  undecomposed  and  partially 
decomposed  blood-corpuscles  were  present  in  large 
quantities.  The  fluid  gave  a  precipitate  of  albumen 
with  nitric  acid,  mercuric  chloride,  and  lead  acetate. 

10.  Electrolysis  of  Albumen. 

When  an  albumen  solution  was  electrolyzed  by 
Dumas  and  Prevost,  under  conditions  similar  to  those 
used  by  Becquerel  for  blood,  the  alkali  metal  went  to 
the  negative  pole,  hydrogen  was  evolved,  and  acetic 
and  phosphoric  acids  appeared  at  the  positive  pole. 
The  result  of  this  is  that  the  albumen  is  coagulated 

1  Chem.  Centralblatt,  1861,  p.  613. 


82       ELECTROLYSIS  AND    ELECTROS YNTHES1S 

at  the  negative  pole  (by  the  alkali  present),  while  at 
the  positive  pole  the  solution  remains  clear. 

As  Lassaigne  has  shown,  pure  albumen  in  aqueous 
solution  is  a  non-conductor  of  electricity;  the  addition 
of  salts  or  acids  is  therefore  necessary  in  its  elec- 
trolysis. 


ii.  Electrolysis  and  Electrosynthesis  with 
Alternating  Currents. 

If  the  polarity  of  the  current  does  not  change 
altogether  too  rapidly,  since  oxidation  and  reduction 
occur  successively  at  each  pole,  it  is  possible  to 
accomplish  electrolyses  and  electrosyntheses  with 
alternating  currents.  Experiments  with  this  end  in 
view  have  been  made  by  Drechsel.1  Dehydration  is 
a  case  of  simultaneous  reduction  and  oxidation.  The 
supposition  that  in  living  organisms  carbamide  is  pro- 
duced from  ammonium  carbamate  by  the  splitting  off 
of  water  prompted  Drechsel  to  make  experiments  in 
this  direction.3 

If  an  aqueous  solution  of  ammonium  carbamate  was 
electrolyzed  with  a  current  from  a  battery  of  4-6 
Grove  elements  and  platinum  electrodes  were  used, 
carbamide  was  obtained  independently  of  the  elec- 


Journ.  prakt.  Chem.,  22,  476. 
Ibid. 


OF  AROMATIC   COMPOUNDS.  83 

trode    material  when    alternating  currents  were    em- 
ployed.    The  reactions  are  supposed  to  be  either 


H2O, 

II.   NH2.CO.ONH,+  2H  =r  NH3.CO.NH,  +  HaO, 
or 

I.   NH2.COONH4  +  2H  =  NHa.CONH4+  H2O, 

II.  NHa.CO.NH4  +  O  =  NHa.CO.NHa  +  H.O. 

The  fact  that  the  platinum  electrodes  were  strongly 
attacked,  with  the  formation  of  platinum  salts,  caused 
Gerdes  '  to  investigate  the  platinum  bases.  As  the 
principal  product  he  found  a  compound  to  which  he 
gave  the  following  formula: 

/ONHJ  p/NH3     NH,0\ 
J\ONH3  }  1  tXNH3     NH30/L 

and  the  chloride  of  which  is  said  to  have  the  composi- 
tion 

CINHXp/NH,     NH3C1        Q 

NH,CI>J:  L1*^    Ha°* 


Gerdes  also  examined  the  nitrate  and  sulphate  of 
this  base. 

In  the  course  of  further  researches2  Drechsel  found 
that  when  alkaline  solutions  were  used  platinum  was 
present  in  the  electrolyzed  fluid.  Copper  when  used 
as  electrode  showed  a  similar  behavior;  lead  was  less 

1  Journ.  prakt.  Chem.,  26,  257. 
*  Ibid.,  29,  229. 


84       ELECTROLYSIS  AND   ELECTRO  SYNTHESIS 

attacked,  gold  but  very  slightly,  and  palladium  not 
at  all. 

The  formation  of  the  phenol  ester  of  sulphuric  acid 
in  living  organisms  is  supposed,  like  carbamide,  to  be 
the  result  of  dehydration.  Taking  this  into  consid- 
eration, Drechsel  carried  out  the  following  experiment: 

A  saturated  solution  of  acid  magnesium  carbonate 
was  mixed  with  an  equal  volume  of  a  solution  of 
magnesium  "sulphate  and  the  mixture  was  saturated 
with  commercial  carbolic  acid.1 

When  this  solution  was  electrolyzed  for  thirty 
hours  with  alternating  currents  and  platinum  elec- 
trodes were  used,  the  following  products  were  ob- 
tained: 

1.  ^-Diphenol.  7.   Succinic  acid. 

2.  Pyrocatechin.  8.   Malonic  acid  (?). 

3.  Hydroquinone.  9.   n-Valeric  acid  (?). 

4.  Phenol    ester    of    sul-      10.   n-Butyric  acid  (?). 

phuric  acid.  n.   Some  cyclohexanone," 

5.  Oxalic  acid.  C6H10O. 

6.  Formic  acid. 

According  to  Drechsel  the  formation  of  the  phenol 
ester  of  sulphuric  acid  is  probably  represented  by  the 
following  equations: 

I.  C6H6OH+HO.SO8H+O=C6H5.OOSO3H+H,O, 
II.   C6H6.OOSO3H  +  2H  =  C6H5.SO3H  +  HaO. 

1  Journ.  prakt.  Chem.,  [2]  29,  229. 

2  Jbib.t  [2]  38,  67. 


OF  AROMATIC  COMPOUNDS.  8$ 

Later  Drechsel '  electrolyzed  normal  capronic  acid 
with  alternating  currents.  The  electrolytic  solution 
contained,  in  a  volume  of  3  liters,  200  g.  of  capronic 
acid  as  magnesium  salt  and  was  nearly  saturated  with 
acid  magnesium  carbonate.  Platinum  electrodes  were 
used.  At  the  end  of  the  experiment  the  following 
compounds  could  be  identified  in  the  solution: 

1.  Valeric  acid.  5.  Adipic  acid. 

2.  Butyric  acid.  6.  Oxy-capronic  acid. 

3.  Oxalic  acid.  7.  Glutaric  acid. 

4.  Succinic  acid. 

In  a  still  later  research  on  the  electrolysis  of  pheno 
with  alternating  currents  Drechsel 2  detected  phenyl- 
sulphuric  acid,  dioxy-benzenes,  a  number  of  acids  of 
the  fatty  acid  series,  arid  in  addition  to  these  an  oil 
which  he  identified  as  hydro-pheno-ketone, 

CH, 

/\ 

H,C      C  :  O 

I       , 
H,C      CH, 

\/ 
CH, 

and  whose  phenylhydrazine  compound  he  was  able  to 
isolate.  Drechsel  regards  the  hydro-pheno-ketone  as 
the  origin  of  the  fatty  compounds  formed.  By  the 

1  Journ.  prakt.  Chem.,  34,  135. 

..  3$,  6$. 


86       ELECTROLYSIS  AND   ELECTROSYNTHESIS. 

direct  addition  of  water  to  this  compound  capronic 
acid  results,  and  this  then  breaks  up  into  the  acids  and 
other  decomposition  products  mentioned  above. 


A  critical  review  of  the  subject-matter  which  has 
here  been  presented  will  bring  out,  concerning  the 
electrolysis  and  electrosynthesis  of  organic  com- 
pounds, several  important  points  which  promise  to 
be  of  great  assistance,  at  no  very  distant  date,  in  con- 
nection with  future  research  in  the  field  of  organic 
chemistry.  These  points  may  be  summarized  as  fol- 
lows: the  oxidation  reactions  which  occur  in  the 
electrolysis  of  acids  of  the  aliphatic  series,  the  reduc- 
tion reactions  in  the  case  of  the  aromatic  series,  and, 
lastly,  the  reactions  involving  substitutions,  concern- 
ing which  but  few  researches  have  been  published. 
Of  these  the  first  is  apparently  the  most  promising. 

Since  in  all  the  experiments  which  have  thus  far 
been  made  the  dependence  of  all  reactions  upon 
current  density,  temperature,  and  concentration  is 
clearly  evident,  the  attention  of  experimenters  is 
again  called  to  the  importance  of  exact  data  con- 
cerning the  conditions  of  experiment. 


AUTHORS. 


PAGE 

Aarland 28 

Ahrens n,  46,  75,  76,  77 

Alessi. 25 

Almeida 2,  4 

Balbiano *    25 

Bartoli 7,  13,  51,  52 

Bauer   18 

Becquerel 3,  81 

Berthelot 44,  45,  49 

Bourgoin 13,  14,  18,  25,  26,  27,  28,  29,  32,  44,  56,  57,  79 

Brazier 24 

Brester 8,  13,  24,  25,  28,  56,  58 

Brown 12,  30,  34,  35,  37,  40,  42,  44,  58 

Buff 44 

Bunge 20,  25,  47,  51,  52,  53,  57 

Christomanos 53 

Classen 6,  25,  31 

Clement 64 

Connel 4 

Deheran 2,  4 

Despretz 18 

Destrem 59 

Dorrance 72 

Drechsel 82,  83,  84,  85 

Dumas 81 

Dupre 18 

87 


88  A  UTHORS. 

PAGE 

Elbs 5,6,  19,  36,  63,  77 

£tard 53 

Pulsing 62 

Friedel 10,  40 

Gattermann 63,  64,  66,  67,  68,  70,  71,  72 

Gay-Lussac 45 

Gerdes 83 

Goppelsroeder 60,  62 

Gossleth 24 

Guthries 37,48 

Habermann 2,  3,  4 

Hamonet 20 

Haussermann 63 

Heilpern 77 

Hemptinne u 

Henderson 40 

Herz 5,  6 

Hittorf 48 

Hof 74 

Hofer 9,  30,  31 

Hof  man  n 44 

Huntington 45 

Jahn 3,  15,  20 

Jaillard 2 

Jovitschitsch 13,  14 

Kauffmann 36,  54,  74 

Kekule 12,  16,  26,  30,  42 

Kemp : 18 

Kendall .' 63 

Kolbe 12,  15,  18,  19,  23,  24,  27,  32,  37,  44,  48 

Koppert 63 

Lapschin 14 

Lassaigne 82 

Liebmann 61 

Lob 6,  16,  57,  63,  66,  68,  73,  74 

Losanitsch 13,  14 

Luckow 46 


A  UTHORS.  89 


Ludersdorf 4 

Maquenne 2,  n 

Mattenci 56 

McCoy 7 

Meissner n 

Messinger 6 

Miller 9,  3°.  3*.  34 

Moore 19 

Mulder 10 

Mulliken 12,  42,  43,  44 

Noyes 64,  72 

Papasogli .' 7.  13,  5i,  52 

Perkin . , 45 

Perrot •' 2,  46 

Pommerehne 78,  79 

Pre  vost 81 

Quet,  M 2 

Reboul 27 

Renard 2,  4,  6,  8,  13,  25,  47,  48 

Richardson 80 

Riche 4,  10 

Rohland 17 

Rotundi,  E 59 

Royer 12 

Schall,  C 16,  48,  49 

Schields 42 

Schlagdenhauffen 45,  46 

Schonbein 3 

Slawik 58 

Smith 1 8 

Stone 7 

Straub 72 

Tichanowitsch 14,  81 

Tommasi 7 

Voigt 62 

Vostmann 

Walker 12,  30,  34,  35,  37.  4O,  42,  44,  58 


QO  A  UTHORS. 

PAGE 

Weems 12,  42,  43,  44 

Weith 4; 

Weizmann 55 

Wiedemann 18 

Wilde 11,13 

Wttrz 24 


INDEX. 


PAGB 

Acetanilide 62 

Acetic  acid... 3,  4,  7,  10,  14,  18,  19,  29,  32,  34,  35,  48,  62,  81 

Acetic  aldehyde 4,  8,  n,  29,  32,  33,  36,  48 

Acetic  ester 3,  4,  15,  34 

Aceto-acetic  ester 43 

Acetone t 10,  32 

Aceto-nitrile 46 

Aceto-phenone 54 

Aceto-phenone  pinacone 54 

Acetyl-acetone 1 1,  43 

Acety  1-dicarboxylic  ester 43 

Acetyl  disulphide 19 

Acetylene 2,  n,  27,  30,  45,  56,  57,  59 

Acetyl-malonic  ester 43 

Acids,  aromatic 56 

Acids,  fatty n,  85 

Acid  superoxides 16,  1 7 

Acid  supersulphides 17 

Acrylic  acid 28 

Adipic  acid 38,  85 

Albumen bi 

Alcohol  aldehydes g 

Alcohols. . .    I,  23,  75 

Aldehyde,  see  acetic  aldehyde. 

Aldehyde-phenyl-hydroxylamines /I 

Aldehyde  resin 4 

Aldeh\dcs 9,  36,  54 


Q2  INDEX. 

PAGE 

Aldol 32 

Alizarine 61 

Alkaloids 78 

Alkyl-oxy-anilines 70 

Allocamphoric  acid 40,  41 

Allylene 28 

Amalic  acid 78 

Amides 43 

Amido-acetone n 

Amido-azo-benzene 62 

Amido-azo-compounds 60 

Amido-benzyl  alcohol 65 

Amido-compounds 59,  63,  75 

Amido-cresol-monosulphuric  acid 64 

Amido-cresotinic  acid 64 

Amido-hydroquinone 62 

Amido-naphthalene-sulphonic  acid 65 

Amido-oxy-acetophenone 71 

Amido-oxy-benzophenone 72 

Amido-oxy-phenyl-p-tolylketone 72 

Amido-phenol-carboxylic  esters 70 

Amido-phenols , 6^,  66,  70,  71,  73 

Amido-phenol  sulphate 63 

Amido-phenol-sulphonic  acid , 64,  73 

Amido-salicylic  acid 64 

Amines 46 

Ammonium  carbamate 82 

Anhydride,  formation  of 16,  29 

Anhydro-hydroxylamine-benzyl  alcohol 68 

Aniline 45,  59,  60,  61,  62,  63,  69 

Aniline  black 60,  61 

Aniline  dyes 60,  62 

Anthraquinone 55,  60,  61 

Aristol 6 

Atropine 78 

Azo-acids 73 

Azo-benzene 63,  77 


INDEX.  93 

PAGE 

Azo-benzoic  acid 74 

Azo-benzyl  alcohol 74 

Azo-  m-benzyl-alcohol-m-benzoic  acid 74 . 

Azo-compounds 59,  63,  72,  74 

Azo-dyes • 74 

Azo-stilbene-disulphonic  acid 75 

Azo-toluene 69 

Azoxy-benzoic  acid 73 

Azoxy-com  pounds 63,  72 

Azoxy-stilbene-disulphonic  acid 75 

Benzaldehyde 33,  35,  36,  54,  57,  67,  68 

Benzene 45 

Benzene-phenylene-diamine 62 

Benzhydrol 54 

Benzidene 63 

Benzile 55 

Benzilic  acid 55 

Benzoic  acid 55,  56 

Benzo-nitrile 47 

Benzoyl-sulphone-imides 77 

Benzylamine 47 

Benzyl-cyanide  47 

Benzylidene  compounds 67 

Benzylidene-phenyl-hydroxylamine , 67 

Benzylidene-tolyl-hydroxylamine 67 

Benzyl-malonic  acid 35,  42,  43,  58 

Blood 81 

Brom-anilines  66 

Brom-maleic  acid. 30 

Bromoform 6 

Brucine  ....    ...     80 

Butane 20 

Butyl  alcohol 4 

Butylene 24 

Butyric  acid 20,  34,  84,  85 

Butyric  ethyl  ester 34 

Butyric  isopropyl  ester...   ,,,, , 21 


94  .  INDEX. 

PAGE 

Caffeine 78 

Campholytic  acid 40 

Camphor 80 

Camphoric  acid 40,  42 

Camphothetic  acid 40 

Cane  sugar 8 

Capronic  acid. 17,  24,  85,  86 

Capronic  amyl  ester 24 

Capronic  ethyl  ester 34 

Caprylic  acid 17 

Carbamide 84 

Carbinoles 75 

Chlor-acetic  acids 4 

Chloral  hydrate 7 

Chlor-anilines , 66,  67 

Chlor-nitro-benzene..  .> 73 

Chloroform 6 

Chrysaniline 62 

Cinchonine 79 

Cinnamic  acid 58 

Cinnamic  aldehyde 4 

Citraconic  acid 28 

Codeine 79 

Collodion 9 

Copellidine 76 

Cotarnine 79 

Cresotinic  acid 78 

Crotonic  acid 40 

Crotonic  aldehyde 32,  33 

Cyan-acetic  acid 19 

Cyan-acetic  ester 43 

Cyanogen 44,  46 

Cyanogen  compounds 44 

Cy  clohexanone 84 

Decahexane-dicarboxylic  acid 38 

Decane 17,  24 

Dehydration 82 


INDEX.  95 


Dextrine 9 

Diacetyl-succinic  ester 43 

Diamido-benzene  sulphate 72 

Diamido-cresol. 64 

Diamido-phenol 64 

Diazo-amido-compounds 59 

Diazo-compounds 59 

Dibenzyl-succinic  ester 35 

Dichlor-acetone 10 

Dicyan-succinic  ester 43 

Diethyl-  ethane-tetracarboxylic  ester 43 

Diethyl-malonic  acid 39,  40 

Diethyl-succinic  acids 39 

Dihydro-quinaldine 76 

Dihydro-quinoline 76 

Di-isobutane 24 

Dimethyl-dithiocarbamic  acid 49 

Dimethylene-ditolidene 69 

Dimethyl-ethane-tetracarboxylic  ester 43 

Dime  thy  1-malonic  acid 39,  40 

Difnethyl-pyrazine,  ketine n 

Dimethyl-succinic  acids 38 

Dimethyl-toluidenes 69 

Dinitro-benzene • 64 

Dinitro-naphthalenes  75 

Dinitro-stilbene-disulphonic  acid 75 

D  in  itro- toluene 64 

Dioxy-anthraquinone 55 

Dioxy-benzenes 85 

Dioxy-benzoic  acid 78 

Diphenol 84 

Diphenyl 53 

Diphenylamine 60,  61 

Dipiperidyl 77 

Disulphides 47 

Dithionic  acids 17 

Di-thymol-di-iodide , , , .  6 


96  INDEX. 


PAGE 

Ditolylamine 60 

Dodecane 17 

Dodecane-dicarboxylic  acid 38 

Dyes,  aniline 60,  62 

Dyes,  orange 74 

Dyes,  triphenyl-methane 75 

Dyes,  yellow  mordant 77 

Esters 36,  38,  39 

Ethane * 2,  4,  u,  15,  16,  18,  19,  29 

Ethane-hexacarboxylic  ester 43 

Ethane-tetracarboxylic  ester 43 

Ethyl  alcohol i,  2,  3,  5,  13,  14,  34,  39 

Ethylamine 46 

Ethyl-crotonic  acid 40 

Ethylene.. 2,  1 8,  20,  27,  32,  36,  42,  45 

Ethylene  cyanide * 19 

Ethylene  glycol 9 

Ethyl-glycolic  acid 36 

Ethylidene  oxy-ethyl  ester 4 

Ethyl-malonic  acid 38 

Ethyl-malonic  ester ...     43 

Ethyl-succinic  ester 35 

Ethyl-sulphuric  acid 4,  48 

Ethyl-tartaric  acid 33 

Formaldehyde 3,  31,  32,  33,  67,  68,  69 

Formamide 14 

Formic  acid 6,  7,  8,  10,  12,  14,  18,  31,  32,  33,  47,  48,  78,  84 

Formic  ester 4 

Formyl  chloride 14 

Fumaric  acid 30,  42 

Furfurane 39 

Gallamide 78 

Gallicacid 78 

Gallic  ethyl  ester 78 

Glucose 6,  7,  8 

Glucosides 80 

Glutaric  acid , . , 27,  28,  38,  85 


INDEX. 


Glyceric  acid ^FNIVCTKWV 7>  33 

Glyceric-aldehyde Vp£ 7 *  *  *       7 

Glycerine ^^AUKO^^:, 6,  7,  8 

Glycolic  acid 6,  7,  25,  31,  34,  36 

Glycols 6,  7,  35 

Grape  sugar 8 

Gum  arabic 9 

Heptylic  acid 17 

Hexane 20,  22 

Hydracrylic  acid 32 

Hydrazo  benzene 63 

Hydrazo-benzoic  acid 73 

Hydrazo-compounds 63,  72 

Hydrobenzoln 35,  36,  54 

Hydrocarbons 12,  37,  etc. 

Hydro-cotarnine 79 

Hydrocyanic  acid 44,  45,  59 

Hydro-phenoketone 85 

Hydroquinone 62,  84 

Hydroquinone  ether , 53 

Hydroxylamine  derivatives 64-68,  71 

lodoform ......       5 

lodo-propionic  acid 37 

Isobuty  1-acetic  acid 34 

Isobutyl-acetic  ethyl  ester 34 

Isobutyric  acid 20,  22 

Isobutyric-isopropyl  ester 22 

Isohexane 22 

Isohydrobenzoin 35,  36,  54 

Isonitroso-acetone 1 1 

Isopropyl  alcohol 21,  22 

Itaconic  acid 28 

Ketones 10,  54 

Lactic  acids 32,  36 

Laurolene 41 

Leukaniline 62 

Maleic  acid , , .30,  42 


98  INDEX, 


PACK 

Malic  acid 28,  33 

Malonic  acid 26,  34,  38,  42,  58,  84 

Malonic  ester 43 

Mandelic  acid 33,  35 1  36 

Mannite 8,  g 

Mannonic  acid 8 

Meconic  acid ,      78 

Mercaptans c .  .47,  53 

Mesaconic  acid , 28 

Methane 3,  13  f  14 

Methyl-acetic  ester 18 

Methyl-acrylic  acid « 40 

Methylal 3 

Methyl  alcohol i,  2,  14,  33 

Methylamine „ , , 78 

Methyl-aniline 60,  61 

Methyl-diphenylainine   61 

Methylene-di-p-anhydro-benzyl  alcohol 68 

Methyl  ether 15 

Methyl-ethyl-piperyl-hydrazine 76 

Methyl-formic  ester 18 

Methyl-glycolic  acid. 33 

Methyl-hydrocinnamic  ester , 35 

Methyl-malonic  acid 38,  43 

Methyl  morphine 7g 

Methyl-piperyl-hydrazine 76 

Methyl-sulphuric  acid , -3,  47 

Michler's  ketone 54 

Monobrom-acetone n 

Monobrom-benzene 53 

Monochlor-acetic  acid 19 

Monochlor-acetone 10 

Monoxy-anthraquinone 55 

Morphine 78,  79 

Naphthazarine 75 

Naphthylamine. 60,  61 

Naphthylamine  violet ,..,,.,,, 60 


INDEX.  99 


Nitramines = 70,  72 

Nitraniline 64,  73 

Nitriles 46 

Nitro-acetophenone 72 

Nitro -aldehydes 56,  70,  71 

Nitro-alkyl-anilines 70 

Nitro- alkyl-toluidenes   ..    , 70 

Nitro-arni  no-benzyl -toluene. 65 

Nitro -benzaldehydes 71,  74 

Nitro-benzene 63,  64,  66,  67,  68 

Nitro-benzene-sulphonic  acid 64 

Nitro- benzoic  acids 64,  67,  73 

Nitro-benzophenone 72 

Nitro-benzyl  alcohol 77 

Nitro-benzylidene-aldehydo-phenyl-hydroxylamine 71 

Nitro-carboxylic  acids,  esters  of 7° 

Nitro  compounds,  oxidation  of 76 

Nit ro-compounds,  reduction  of 63 

Nitro-ethane , .  * 37 

Nitro-groups 37,  65,  76 

Nitro-hydrocarbons 72 

Nitro-isophthalic  acid 64 

Nitro-ketones , 56,  71 

Nitro-leuco-bodies 75 

Nitro-naphthaiene-sulphonic  acid 65 

Nitro-phenol. 63,  73 

Nitro-phenyl-tolylketone 72 

Nitro-piperidines 76 

Nitroso-aldehyde-copellidine ". 76 

Nitroso-alkyl-anilines 70 

Nitroso-alkyl-toluidenes, 70 

Nitroso-groups k 76 

Nitroso-pipecoline 76 

Nitroso-piperidine * 76 

Nitro-sulphon ic  acids 70 

Nitro-terephthalic  acid 64 

Nitro-toluenes 64,  65,  67,  69,  70,  77 


1OO  INDEX. 

PAGE 

Nitro-toluene-sulphone-amide 77 

Nitro-toluene-sulphonic  acid 74 

Nitro-toluic  acid „ 64 

Nitroxylene 67 

Nosophene 6 

Octane 24 

Octylene 17 

CEnanthylic  acid    24 

Olefines 23 

Oleic  acid 17 

Opium 78 

Oxalic  acid 8,  10,  12,  25,  42,  84,  85 

Oxy-acids 35,  36 

Oxy-anilines 70 

Oxy-benzoic  acids. 78 

Oxy-butyric  acids 32 

Oxy-capronic  acid 85 

Oxy-carboxylic  acids 78 

Oxy-dimorphine  sulphate 79 

Oxy-isobuty ric  acids .    . . , 32 

Oxy-pyrone-dicarboxylic  acid 78 

Phenol 51,  61,  84,  85 

Phenol-sulphuric  acid 84 

Phenyl-acetic  acid 58 

Phenyl-chloramine , 67 

Phenyl-disulphide 53 

Phenylene-diamine 62,  63 

Phenyl-ethylamine 47 

Phenyl-glyceric  acid 33 

Phenyl-hydroxylamine 64,  66,  67,  68 

Phenyl-lactic  acid 33 

Phenyl-mercaptan 53 

Phenyl-sulphuric  acid 85 

Phenyltolylamine , 60 

Phthalic  acid 16,  42,  57 

Picoline 75 

Picric  acid 52 


INDEX.  10 1 

PAGE 

Pipecoline 75.  ?6 

Piperidine 75,  76 

Piperylhydrazines 76 

Potassium  cyanate 45 

Potassium  cyanide 45 

Potassium  ferricyanide 46 

Potassium  ferrocyanide 44  >  45 

Potassium-isoamyl  sulphate. 48 

Potassium-trichlor-methyl  sulphate 47 

Potassium-trichlor- methyl  sulphonate 48 

Potassium  xanthate 48 

Propionic  acid 20,  34,  36,  37 

Propionic  aldehyde 32 

Propionic  ethyl  ester 34 

Propio-  nitrile 47 

Propyl  alcohol 4,  22 

Propylamine 47 

Propylene 20,  21,  22,  28 

Propylene  bromide 21,  22 

Prussian  blue 45,  46 

Pyrazine II 

Pyridine 75 

Pyrocatechin 84 

Pyrotartaric  acid. 27 

Quinaldine 76 

Quinine 79 

Quinoline ...70,  76 

Quinone 61,  62 

Racemic  acid 33 

Resinous  bodies , 7,  21,  32,  33,  52,  58 

Rosaniline 62 

Saccharic  acid 8 

Saccharic  aldehyde 8 

Saccharine 77 

Safranine   62 

Salicine 81 

Salicvlic  acid 81 


102  INDEX. 

fAGR 

Salicylic  aldehyde 81 

Sebacfc  acid 7,  38,  40 

Sodium-diethyl-malonic  ester 43 

Sodium-isethionate 47 

Sodium-methane-tricarboxylic  ester 43 

Sodium-nitro-prusside 46 

Starch 9 

Strychnine 80 

Suberic  acid 38 

Succinic  acid 26,  30,  34,  37,  38,  84,  85 

Sugars 8 

Sulpho-benzoic  acid 57 

Sulpho-compounds 47 

Tannin 78 

Tartaric  acid 29,  32 

Terpentine  hydrochloride ....     80 

Tetracetyl-ethane 1 1 ,  43 

Tetradecane , 17 

Tetraethyl-succinic  acid 39 

Tetraethyl-thiuramdisulphide 49 

Tetrahydro-quinaldine 76 

Tetrahydro-quinoline 76 

Tetra-iodo-phenol-phthalein 6 

Tetramethyl-di-amido-benzophenone 54 

Tetramethyl-succinic  acid 38,  39 

Tetraoxy-azo-benzene. . .    77 

Tetraphenyl-erythrite 55 

Theine 78 

Thio-acetic  acid 19 

Thio-benzoic  acid 57 

Thiophene 49 

Thymol , 6 

Toluene-sulphone-amides 77 

Toluic  acids , 61 

Toluidenes 60,  61,  69 

Tolyl-hydroxylamines = 65 

Tricarballylic  ester. 34 


INDEX.  103 

PAGE 

Trichlor-acetic  acid 19 

Trichlor-methyl  ester 19 

Trioxy-anthraquinone 55 

Trioxy-methy lene 6,  7,  8,  47 

Triphenyl-methane  dyes 75 

Undecylenic  acid 17 

Unsaturated  acids 17,  42 

Unsaturated  esters 39 

Unsaturated  hydrocarbons 17,  33,  42 

Valeric  acids 24,  48,  84,  85 

Valeric  butyl  ester. ...;    , 24 

Valeric  ethyl  ester 34, 

Xanthogen  supersulphide 48 


SHORT-TITLE   CATALOGUE 

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8 


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9 


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12 


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3.73 


